U.S. patent application number 10/501882 was filed with the patent office on 2005-06-30 for aromatic polycarbonate resin, process for producing the same, optical-part molding material, and optical part.
This patent application is currently assigned to Idemitsu Kosan Co., Ltd. Invention is credited to Hamada, Yasushi, Morishita, Hironobu, Tamura, Hiroyuki.
Application Number | 20050143553 10/501882 |
Document ID | / |
Family ID | 27617300 |
Filed Date | 2005-06-30 |
United States Patent
Application |
20050143553 |
Kind Code |
A1 |
Morishita, Hironobu ; et
al. |
June 30, 2005 |
Aromatic polycarbonate resin, process for producing the same,
optical-part molding material, and optical part
Abstract
The present invention relates to an aromatic polycarbonate resin
which comprises repetitive units originating in residual groups of
a 2,2-bis(4-hydroxyphenyl)adamantane compound and a
1,3-bis(4-hydroxyphenyl- )adamantane compound having a substituent
on an aromatic ring and which is excellent in a transparency, a
heat resistance and a mechanical strength and has a good
moldability and a production process for the aromatic polycarbonate
resin described above in which the adamantane compounds described
above are reacted with a carbonic ester-forming compound. Further,
it relates to an aromatic polycarbonate resin which is excellent in
an optical characteristic and an optical part prepared by molding
the same.
Inventors: |
Morishita, Hironobu;
(Sodegaura-shi, JP) ; Tamura, Hiroyuki;
(Sodegaura-shi, JP) ; Hamada, Yasushi;
(Sodegaura-shi, JP) |
Correspondence
Address: |
PARKHURST & WENDEL, L.L.P.
1421 PRINCE STREET
SUITE 210
ALEXANDRIA
VA
22314-2805
US
|
Assignee: |
Idemitsu Kosan Co., Ltd
1-1, Marunouchi 3-chome
Chiyoda-ku
JP
|
Family ID: |
27617300 |
Appl. No.: |
10/501882 |
Filed: |
August 24, 2004 |
PCT Filed: |
January 21, 2003 |
PCT NO: |
PCT/JP03/00471 |
Current U.S.
Class: |
528/196 ;
G9B/7.172 |
Current CPC
Class: |
G11B 7/2534 20130101;
C08G 64/06 20130101 |
Class at
Publication: |
528/196 |
International
Class: |
C08G 064/00 |
Foreign Application Data
Date |
Code |
Application Number |
Jan 23, 2002 |
JP |
2002-013943 |
Jan 28, 2002 |
JP |
2002-018675 |
Feb 7, 2002 |
JP |
2002-030247 |
Claims
1. An aromatic polycarbonate resin which comprises a repetitive
unit (I-1) represented by the following Formula (I-1): 31(wherein
R.sup.1 represents a group selected from the group of a halogen
atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group
having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon
atoms, an aryl-substituted alkenyl group having 7 to 13 carbon
atoms and a fluoroalkyl group having 1 to 6 carbon atoms; R.sup.2
represents a group selected from the group of a halogen atom, an
alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1
to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an
aryl-substituted alkenyl group having 7 to 13 carbon atoms and a
fluoroalkyl group having 1 to 12 carbon atoms; m represents an
integer of 0 to 4; and n represents an integer of 0 to 14) and a
repetitive unit (I-2) represented by the following Formula (I-2):
32(wherein R.sup.3 represents a group selected from the group of a
halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy
group having 1 to 12 carbon atoms, an aryl group having 6 to 12
carbon atoms, an aryl-substituted alkenyl group having 7 to 13
carbon atoms and a fluoroalkyl group having 1 to 12 carbon atoms; X
represents a single bond, --O--, --CO--, --S--, --SO, --SO.sub.2--,
--C(R.sup.4R.sup.5)-- (provided that R.sup.4 and R.sup.5 each
represent independently a hydrogen atom, an alkyl group having 1 to
6 carbon atoms, a phenyl group or a trifluoromethyl group), a
substituted or non-substituted cycloalkylidene group having 6 to 12
carbon atoms, a 9,9'-fluorenylidene group, a 1,8-menthanediyl
group, a 2,8-menthanediyl group, a substituted or non-substituted
pyrazylidene group, a substituted or non-substituted arylene group
having 6 to 12 carbon atoms
or--C(CH.sub.3).sub.2-ph-C(CH.sub.3).sub.2-- (provided that ph
represents a phenylene group); and p represents an integer of 0 to
4) and in which the solution having a concentration of 0.5
g/deciliter using methylene chloride as a solvent has a reduced
viscosity (.eta..sub.sp/c) of 0.1 deciliter/g or more which is
measured at 20.degree. C.
2. The aromatic polycarbonate resin as described in claim 1,
wherein the repetitive unit (I-2) is represented by the following
Formula (I-3): 33wherein R.sup.3, X and p each represent the same
as R.sup.3, X and p in Formula (I-2).
3. The aromatic polycarbonate resin as described in claim 1,
wherein R.sup.1 in Formula (I-1) is an alkyl group having 1 to 6
carbon atoms.
4. The aromatic polycarbonate resin as described in claim 1,
wherein X in Formula (I-2) is --C(R.sup.4R.sup.5)-- (provided that
R.sup.4 and R.sup.5 each represent independently a hydrogen atom,
an alkyl group having 1 to 6 carbon atoms, a phenyl group or a
trifluoromethyl group), a substituted or non-substituted
cycloalkylidene group having 6 to 12 carbon atoms or a
9,9'-fluorenylidene group.
5. A production process for the aromatic polycarbonate resin as
described in claim 1, characterized by reacting a
2,2-bis(4-hydroxyphenyl)adamantan- e compound represented by the
following Formula (I-4): 34herein R.sup.1 represents a group
selected from the group of a halogen atom, an alkyl group having 1
to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an
aryl group having 6 to 12 carbon atoms, an aryl-substituted alkenyl
group having 7 to 13 carbon atoms and a fluoroalkyl group having 1
to 6 carbon atoms; R.sup.2 represents a group selected from the
group of a halogen atom, an alkyl group having 1 to 12 carbon
atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group
having 6 to 12 carbon atoms, an aryl-substituted alkenyl group
having 7 to 13 carbon atoms and a fluoroalkyl group having 1 to 12
carbon atoms; m represents an integer of 0 to 4; and n represents
an integer of 0 to 14) and divalent phenol represented by the
following Formula (I-5): 35(wherein R.sup.3 represents a group
selected from the group of a halogen atom, an alkyl group having 1
to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an
aryl group having 6 to 12 carbon atoms, an aryl-substituted alkenyl
group having 7 to 13 carbon atoms and a fluoroalkyl group having 1
to 12 carbon atoms; X represents a single bond, --O--, --CO--,
--S--, --SO, --SO.sub.2--, --C(R.sup.4R.sup.5)-- (provided that
R.sup.4 and R.sup.5 each represent independently a hydrogen atom,
an alkyl group having 1 to 6 carbon atoms, a phenyl group or a
trifluoromethyl group), a substituted or non-substituted
cycloalkylidene group having 6 to 12 carbon atoms, a
9,9'-fluorenylidene group, a 1,8-menthanediyl group, a
2,8-menthanediyl group, a substituted or non-substituted
pyrazylidene group, a substituted or non-substituted arylene group
having 6 to 12 carbon atoms or
--C(CH.sub.3).sub.2-ph-C(CH.sub.3).sub.2-- (provided that ph
represents a phenylene group); and p represents an integer of 0 to
4) with a carbonic ester-forming compound.
6. The production process for the aromatic polycarbonate resin as
described in claim 5, wherein a compound represented by the
following Formula (I-6) is used as the divalent phenol: 36wherein
R.sup.3, X and p each represent the same as R.sup.3, X and p in
Formula (I-5).
7. The production process for the aromatic polycarbonate resin as
described in claim 5, wherein the compound in which R.sup.1 in
Formula (I-4) is an alkyl group having 1 to 6 carbon atoms is used
as the 2,2-bis(4-hydroxyphenyl)adamantane compound.
8. The production process for the aromatic polycarbonate resin as
described in claim 5, wherein used as the divalent phenol is the
compound in which X in Formula (I-5) is
--C(R.sup.4R.sup.5)--(provided that R.sup.4 and R.sup.5 each
represent independently a hydrogen atom, an alkyl group having 1 to
6 carbon atoms, a phenyl group or a trifluoromethyl group), a
substituted or non-substituted cycloalkylidene group having 6 to 12
carbon atoms or a 9,9'-fluorenylidene group.
9. An aromatic polycarbonate resin which comprises a repetitive
unit represented by the following Formula (II-1): 37wherein R.sup.1
represents a group selected from the group of a halogen atom, an
alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to
6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an
aryl-substituted alkenyl group having 7 to 13 carbon atoms and a
fluoroalkyl group having 1 to 6 carbon atoms; and m represents an
integer of 1 to 4) and in which the solution having a concentration
of 0.5 g/deciliter using methylene chloride as a solvent has a
reduced viscosity (.eta..sub.sp/c) of 0.1 deciliter/g or more which
is measured at 20.degree. C.
10. The aromatic polycarbonate resin as described in claim 9,
wherein R.sup.1 in Formula (II-1) is an alkyl group having 1 to 6
carbon atoms.
11. An aromatic polycarbonate resin which comprises a repetitive
unit (II-1) represented by the following Formula (II-2): 38wherein
R.sup.2 represents a group selected from the group of a halogen
atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group
having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon
atoms, an aryl-substituted alkenyl group having 7 to 13 carbon
atoms and a fluoroalkyl group having 1 to 6 carbon atoms; and n is
an integer of 1 to 4) and a repetitive unit (II-2) represented by
the following Formula (II-3): 39(wherein R.sup.3 represents a group
selected from the group of a halogen atom, an alkyl group having 1
to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an
aryl group having 6 to 12 carbon atoms, an aryl-substituted alkenyl
group having 7 to 13 carbon atoms and a fluoroalkyl group having 1
to 12 carbon atoms; and X represents a single bond, --O--, --CO--,
--S--, --SO--, --SO.sub.2--, --C(R.sup.4R.sup.5)-- (provided that
R.sup.4 and R.sup.5 each represent independently a hydrogen atom,
an alkyl group having 1 to 6 carbon atoms, a phenyl group or a
trifluoromethyl group), a substituted or non-substituted
cycloalkylidene group having 6 to 12 carbon atoms, a
9,9'-fluorenylidene group, a 1,8-menthanediyl group, a
2,8-menthanediyl group, a substituted or non-substituted
pyrazylidene group, a substituted or non-substituted arylene group
having 6 to 12 carbon atoms or
--C(CH.sub.3).sub.2-ph-C(CH.sub.3).sub.2-- (provided that ph
represents a phenylene group); and p represents an integer of 0 to
4) and in which the solution having a concentration of 0.5
g/deciliter using methylene chloride as a solvent has a reduced
viscosity (.eta..sub.sp/c) of 0.1 deciliter/g or more which is
measured at 20.degree. C.
12. The aromatic polycarbonate resin as described in claim 11,
wherein the repetitive unit (II-2) is represented by the following
Formula (II-4): 40wherein R.sup.3, X and p each represent the same
as R.sup.3, X and p in Formula (II-3).
13. The aromatic polycarbonate resin as described in claim 11,
wherein R.sup.2 in Formula (II-2) is an alkyl group having 1 to 6
carbon atoms.
14. The aromatic polycarbonate resin as described in claim 11,
wherein X in Formula (II-3) is --C(R.sup.4R.sup.5)-- (provided that
R.sup.4 and R.sup.5 each represent independently a hydrogen atom,
an alkyl group having 1 to 6 carbon atoms, a phenyl group or a
trifluoromethyl group), a substituted or non-substituted
cycloalkylidene group having 6 to 12 carbon atoms or a
9,9'-fluorenylidene group.
15. A production process for the aromatic polycarbonate resin as
described in claim 9, characterized by reacting a
1,3-bis(4-hydroxyphenyl)adamantan- e compound represented by the
following Formula (II-5): 41(wherein R.sup.1 represents a group
selected from the group of a halogen atom, an alkyl group having 1
to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an
aryl group having 6 to 12 carbon atoms, an aryl-substituted alkenyl
group having 7 to 13 carbon atoms and a fluoroalkyl group having 1
to 6 carbon atoms; and m represents an integer of 1 to 4) with a
carbonic ester-forming compound.
16. The production process for the aromatic polycarbonate resin as
described in claim 15, wherein the compound in which R.sup.1 in
Formula (II-5) is an alkyl group having 1 to 6 carbon atoms is used
as the 1,3-bis(4-hydroxyphenyl)adamantane compound.
17. A production process for the aromatic polycarbonate resin as
described in claim 11, characterized by reacting a
1,3-bis(4-hydroxyphenyl)adamanta- ne compound represented by the
following Formula (II-6): 42(wherein R.sup.2 represents a group
selected from the group of a halogen atom, an alkyl group having 1
to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an
aryl group having 6 to 12 carbon atoms, an aryl-substituted alkenyl
group having 7 to 13 carbon atoms and a fluoroalkyl group having 1
to 6 carbon atoms; and n represents an integer of 1 to 4) and
divalent phenol represented by the following Formula (II-7):
43(wherein R.sup.3 represents a group selected from the group of a
halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy
group having 1 to 12 carbon atoms, an aryl group having 6 to 12
carbon atoms, an aryl-substituted alkenyl group having 7 to 13
carbon atoms and a fluoroalkyl group having 1 to 12 carbon atoms; X
represents a single bond, --O--, --CO--, --S--, --SO, --SO.sub.2--,
--C(R.sup.4R.sup.5)-- (provided that R.sup.4 and R.sup.5 each
represent independently a hydrogen atom, an alkyl group having 1 to
6 carbon atoms, a phenyl group or a trifluoromethyl group), a
substituted or non-substituted cycloalkylidene group having 6 to 12
carbon atoms, a 9,9'-fluorenylidene group, a 1,8-menthanediyl
group, a 2,8-menthanediyl group, a substituted or non-substituted
pyrazylidene group, a substituted or non-substituted arylene group
having 6 to 12 carbon atoms or --C(CH.sub.3).sub.2-ph-C(CH.-
sub.3).sub.2-- (provided that ph represents a phenylene group); and
p represents an integer of 0 to 4) with a carbonic ester-forming
compound.
18. The production process for the aromatic polycarbonate resin as
described in claim 17, wherein the compound in which R.sup.2 in
Formula (II-6) is an alkyl group having 1 to 6 carbon atoms is used
as the 1,3-bis(4-hydroxyphenyl)adamantane compound.
19. The production process for the aromatic polycarbonate resin as
described in claim 17, wherein a compound represented by the
following Formula (II-8) is used as the divalent phenol: 44wherein
R.sup.3, X and p each represent the same as R.sup.3, X and p in
Formula (II-7).
20. The production process for the aromatic polycarbonate resin as
described in claim 17, wherein used as the divalent phenol is the
compound in which X in Formula (II-7) is
--C(R.sup.4R.sup.5)--(provided that R.sup.4 and R.sup.5 each
represent independently a hydrogen atom, an alkyl group having 1 to
6 carbon atoms, a phenyl group or a trifluoromethyl group), a
substituted or non-substituted cycloalkylidene group having 6 to 12
carbon atoms or a 9,9'-fluorenylidene group.
21. An optical part-molding material comprising an aromatic
polycarbonate resin which comprises a repetitive unit represented
by the following Formula (III-1): 45(wherein R.sup.1 and R.sup.2
each represent independently a group selected from the group of a
halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy
group having 1 to 6 carbon atoms, an aryl group having 6 to 12
carbon atoms, an aryl-substituted alkenyl group having 7 to 13
carbon atoms and a fluoroalkyl group having 1 to 6 carbon atoms;
R.sup.3 represents a group selected from the group of a halogen
atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group
having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon
atoms, an aryl-substituted alkenyl group having 7 to 13 carbon
atoms and a fluoroalkyl group having 1 to 12 carbon atoms; a and b
represent an integer of 0 to 4; and c represents an integer of 0 to
14) and in which the solution having a concentration of 0.5
g/deciliter using methylene chloride as a solvent has a reduced
viscosity (.eta..sub.sp/c) of 0.1 deciliter/g or more which is
measured at 20.degree. C.
22. The optical part-molding material as described in claim 21,
wherein R.sup.1 and R.sup.2 in Formula (III-1) are alkyl groups
having 1 to 6 carbon atoms.
23. The optical part-molding material comprising the aromatic
polycarbonate resin as described in claim 21, wherein the
repetitive unit is represented by the following Formula (III-2):
46wherein R.sup.1, R.sup.2, R.sup.3, a, b and c each represent the
same as R.sup.1, R.sup.2, R.sup.3, a, b and c in Formula
(III-1).
24. The optical part-molding material as described in claim 23,
wherein R.sup.1 and R.sup.2 in Formula (III-2) are alkyl groups
having 1 to 6 carbon atoms.
25. An optical part-molding material comprising an aromatic
polycarbonate resin which comprises a repetitive unit (III-1)
represented by the following Formula (III-3): 47(wherein R.sup.4
and R.sup.5 each represent independently a group selected from the
group of a halogen atom, an alkyl group having 1 to 6 carbon atoms,
an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6
to 12 carbon atoms, an aryl-substituted alkenyl group having 7 to
13 carbon atoms and a fluoroalkyl group having 1 to 6 carbon atoms;
R.sup.6 represents a group selected from the group of a halogen
atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group
having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon
atoms, an aryl-substituted alkenyl group having 7 to 13 carbon
atoms and a fluoroalkyl group having 1 to 12 carbon atoms; d and e
represent an integer of 0 to 4; and f represents an integer of 0 to
14) and a repetitive unit (III-2) represented by the following
Formula (III-4): 48(wherein R.sup.7 and R.sup.8 each represent
independently a group selected from the group of a halogen atom, an
alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1
to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an
aryl-substituted alkenyl group having 7 to 13 carbon atoms and a
fluoroalkyl group having 1 to 12 carbon atoms; X represents a
single bond, --O--, --CO--, --S--, --SO--, --SO.sub.2--,
--C(R.sup.9R.sup.10)-- (provided that R.sup.9 and R.sup.10 each
represent independently a hydrogen atom, an alkyl group having 1 to
6 carbon atoms, a phenyl group or a trifluoromethyl group), a
substituted or non-substituted cycloalkylidene group having 6 to 12
carbon atoms, a 9,9'-fluorenylidene group, a 1,8-menthanediyl
group, a 2,8-menthanediyl group, a substituted or non-substituted
pyrazylidene group, a substituted or non-substituted arylene group
having 6 to 12 carbon atoms,
--C(CH.sub.3).sub.2-ph-C(CH.sub.3).sub.2--(provided that ph
represents a phenylene group) or the following Formula (III-5) or
(III-6): 49(wherein R.sup.11 and R.sup.12 each represent
independently a group selected from the group of a halogen atom, an
alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1
to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an
aryl-substituted alkenyl group having 7 to 13 carbon atoms and a
fluoroalkyl group having 1 to 12 carbon atoms; and i and j each
represent an integer of 0 to 14); and g and h each represent an
integer of 0 to 4) and in which the solution having a concentration
of 0.5 g/deciliter using methylene chloride as a solvent has a
reduced viscosity (.eta..sub.sp/c) of 0.1 deciliter/g or more which
is measured at 20.degree. C.
26. The optical part-molding material as described in claim 25,
wherein R.sup.4 and R.sup.5 in Formula (III-3) are alkyl groups
having 1 to 6 carbon atoms.
27. The optical part-molding material as described in claim 25,
wherein the repetitive unit (III-2) is represented by the following
Formula (III-7): 50wherein R.sup.7, R.sup.8, X, g and h each
represent the same as R.sup.7, R.sup.8, X, g and h in Formula
(III-4).
28. The optical part-molding material as described in claim 25,
wherein X in Formula (III-4) is --C(R.sup.9R.sup.10)-- (provided
that R.sup.9 and R.sup.10 each represent independently a hydrogen
atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group or
a trifluoromethyl group), a substituted or non-substituted
cycloalkylidene group having 6 to 12 carbon atoms or a
9,9'-fluorenylidene group.
29. An optical part prepared by molding the optical part-molding
material as described in claim 21.
Description
TECHNICAL FIELD
[0001] The present invention comprises the first invention, the
second invention and the third invention, and the first invention
and the second invention relate to an aromatic polycarbonate resin
and a production process for the same, more specifically to an
aromatic polycarbonate resin which is excellent in a transparency,
a heat resistance and a mechanical strength and which has a good
moldability and an effective production process for the same. The
third invention relates to an optical part-molding material and an
optical part, more specifically to an optical part-molding material
suited to a molding material for an optical disc substrate such as
a digital audio disc, a digital video disc and an optical memory
disc, various lenses such as a lens for an optical pickup,
spectacle lenses, contact lenses and a lens sheet, an optical sheet
substrate such as a prism, a mirror, an optical fiber, a liquid
crystal display and a portable key sheet and an optical functional
element such as a light guiding substance, a reflection film, a
light scattering sheet, a polarizing plate and a phase difference
plate and an optical part prepared by molding the same.
BACKGROUND ART
[0002] Referring to the first invention and the second invention,
an aromatic polycarbonate resin is excellent in properties such as
a transparency, a heat resistance and a mechanical strength, and
therefore it is widely used as a so-called engineering plastic in
various industrial fields. In general, an aromatic polycarbonate
resin produced by reacting 2,2-bis(4-hydroxyphenyl)propane (common
name: bisphenol A) with a carbonic ester-forming compound such as
phosgene and diphenyl carbonate is used as the above aromatic
polycarbonate resin. Because of a good balance of a transparency
and a mechanical strength with a moldability, an aromatic
polycarbonate resin produced using this bisphenol A as a raw
material is used as a raw material for electric and electronic
equipments and optical equipments in many cases. In recent years,
these equipments are increasingly demanded to be decreased in a
size and a weight, and an aromatic polycarbonate resin which is
further improved in characteristics such as a heat resistance and a
mechanical strength without reducing basic characteristics endowed
to this aromatic polycarbonate resin is requested to be developed
in order to meet the above demand.
[0003] Then, in order to meet the above demand, it has been tried
to obtain an aromatic polycarbonate resin which is improved further
more in a heat resistance and a mechanical strength by using
compounds having various structures as a divalent phenol which is a
raw material for an aromatic polycarbonate resin. For example, an
aromatic polycarbonate resin using a raw material of a bisphenol
derivative of adamantane as divalent phenol is proposed in Soobsch.
Akad. Nauk Gruz. SSR (1977), 88(3), p. 597 to 600. This aromatic
polycarbonate resin in which an adamantane skeleton is introduced
into a structural unit of an aromatic polycarbonate polymer chain
has a high heat resistance but has the difficulties that it has a
poor solubility in solvents because it is liable to be crystallized
and it is inferior in a moldability and that the molded article is
reduced in a transparency. Further, proposed are aromatic
polycarbonate resins using a raw material of
1,1-bis(4-hydroxyphenyl)cyclohexane and
9,9'-bis(4-hydroxyphenyl)fluorene alone or in combination with
bisphenol A as divalent phenol. However, these aromatic
polycarbonate resins comprising a structural unit having a residue
of divalent phenol has a higher heat resistance than that of an
aromatic polycarbonate resin using bisphenol A as a raw material,
but further higher heat resistance is required in the production
steps of electric and electronic equipment parts. Thus, when used
as a raw material for electric and electronic equipments and
optical equipment parts, an aromatic polycarbonate resin which has
further higher transparency, heat resistance and mechanical
strength and which is excellent in a moldability is required to be
developed.
[0004] An object of the first invention and the second invention is
to provide an aromatic polycarbonate resin which is excellent in a
transparency, a heat resistance and a mechanical strength and which
has a good moldability and a production process for the same.
[0005] Referring to the third invention, various plastics are
proposed as an optical part-molding material. Characteristics such
as a heat resistance, an impact resistance, a mechanical strength
and an optical property are required to the above optical
part-molding material, and engineering plastics such as polymethyl
methacrylate, polycarbonate using 2,2-bis(4-hydroxyphenyl)propane
as a raw material, polyacrylate and polyethersulfone have so far
been used as materials satisfying the above requirements.
[0006] On the other hand, some of a large number of these optical
parts have a high transparency and require a very high heat
resistance. For example, a liquid crystal display substrate of an
active matrix mode in which a thin film transistor is arranged as a
switching element for every picture element on a glass substrate in
a matrix form and actuated is adopted in many cases. In a
production step of the above liquid crystal display, an electrical
insulating layer of silicon nitride has to be formed by a glow
discharge deposition method when forming a thin film transistor on
a substrate. Accordingly, since the substrate of the above liquid
crystal display is glass, it is liable to be broken by impact
exerted from the outside such as falling, and therefore it is
desired to use a substrate of an engineering plastic having an
excellent impact resistance. In the above engineering plastics,
however, a heat resistance and an impact resistance are not
satisfactory in, for example, polymethyl methacrylate, and a heat
resistance in forming an electrical insulating layer is not
necessarily satisfactory in polycarbonate and polyacrylate.
Further, polyethersulfone has the difficulties that it has a high
heat resistance but is colored amber and that optical anisotropy is
liable to be brought about by slight molecular orientation.
[0007] Thus, an optical part-molding material which is excellent in
a heat resistance and a mechanical strength in addition to an
optical characteristic is requested to be developed as a molding
material for optical parts.
[0008] An object of the third invention is to provide an optical
part-molding material which is excellent in an optical
characteristic and a mechanical strength and which has a
particularly high heat resistance and an optical part prepared by
molding the same.
DISCLOSURE OF THE INVENTION
[0009] I. First Invention
[0010] Intensive researches repeated by the present inventors in
order to solve the problems described above have resulted in
finding that the object described above can be achieved by an
aromatic polycarbonate resin obtained by reacting specific divalent
phenols having an adamantane skeleton and divalent phenols having
various chemical structures with a carbonic ester-forming compound,
and they have come to complete the present first invention based on
the above knowledge.
[0011] That is, the essential point of the first invention is
described below.
[0012] (1) An aromatic polycarbonate resin which comprises a
repetitive unit (I-1) represented by the following Formula [I-1]:
1
[0013] (wherein R.sup.1 represents a group selected from the group
of a halogen atom, an alkyl group having 1 to 6 carbon atoms, an
alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to
12 carbon atoms, an aryl-substituted alkenyl group having 7 to 13
carbon atoms and a fluoroalkyl group having 1 to 6 carbon atoms;
R.sup.2 represents a group selected from the group of a halogen
atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group
having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon
atoms, an aryl-substituted alkenyl group having 7 to 13 carbon
atoms and a fluoroalkyl group having 1 to 12 carbon atoms; m
represents an integer of 0 to 4; and n represents an integer of 0
to 14) and a repetitive unit (I-2) represented by the following
Formula [I-2]:
[0014] (wherein R.sup.3 represents a group selected from the group
of a halogen atom, an alkyl group having 1 to 12 carbon atoms, an
alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to
12 carbon atoms, an aryl-substituted alkenyl group having 7 to 13
carbon atoms and a fluoroalkyl group having 1 to 12 carbon atoms; X
represents a single bond, --O--, --CO--, --S--, --SO--,
--SO.sub.2--, --C(R.sup.4R.sup.5)-- (provided that R.sup.4 and
R.sup.5 each represent independently a hydrogen atom, an alkyl
group having 1 to 6 carbon atoms, a phenyl group or a
trifluoromethyl group), a substituted or non-substituted
cycloalkylidene group having 6 to 12 carbon atoms, a
9,9'-fluorenylidene group, a 1,8-menthanediyl group, a
2,8-menthanediyl group, a substituted or non-substituted
pyrazylidene group, a substituted or non-substituted arylene group
having 6 to 12 carbon atoms or --C(CH.sub.3).sub.2--ph--C(C-
H.sub.3).sub.2-- (provided that ph represents a phenylene group);
and p represents an integer of 0 to 4) and in which the solution
having a concentration of 0.5 g/deciliter using methylene chloride
as a solvent has a reduced viscosity (.eta..sub.sp/c) of 0.1
deciliter/g or more which is measured at 20.degree. C.
[0015] (2) The aromatic polycarbonate resin as described in the
above item (1), wherein the repetitive unit (I-2) is represented by
the following Formula [I-3]: 2
[0016] wherein R.sup.3, X and p each represent the same as R.sup.3,
X and p in Formula [I-2].
[0017] (3) The aromatic polycarbonate resin as described in the
above item (1) or (2), wherein R.sup.1 in Formula [I-1] is an alkyl
group having 1 to 6 carbon atoms.
[0018] (4) The aromatic polycarbonate resin as described in any of
the above items (1) to (3), wherein X in Formula [I-2] is
--C(R.sup.4R.sup.5)-- (provided that R.sup.4 and R.sup.5 each
represent independently a hydrogen atom, an alkyl group having 1 to
6 carbon atoms, a phenyl group or a trifluoromethyl group), a
substituted or non-substituted cycloalkylidene group having 6 to 12
carbon atoms or a 9,9'-fluorenylidene group.
[0019] (5) A production process for the aromatic polycarbonate
resin as described in the above item (1), characterized by reacting
a 2,2-bis(4-hydroxyphenyl)adamantane compound represented by the
following Formula [I-4]: 3
[0020] (wherein R.sup.1 represents a group selected from the group
of a halogen atom, an alkyl group having 1 to 6 carbon atoms, an
alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to
12 carbon atoms, an aryl-substituted alkenyl group having 7 to 13
carbon atoms and a fluoroalkyl group having 1 to 6 carbon atoms;
R.sup.2 represents a group selected from the group of a halogen
atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group
having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon
atoms, an aryl-substituted alkenyl group having 7 to 13 carbon
atoms and a fluoroalkyl group having 1 to 12 carbon atoms; m
represents an integer of 0 to 4; and n represents an integer of 0
to 14) and divalent phenol represented by the following Formula
[I-5]: 4
[0021] (wherein R.sup.3 represents a group selected from the group
of a halogen atom, an alkyl group having 1 to 12 carbon atoms, an
alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to
12 carbon atoms, an aryl-substituted alkenyl group having 7 to 13
carbon atoms and a fluoroalkyl group having 1 to 12 carbon atoms; X
represents a single bond, --O--, --CO--, --S--, --SO--,
--SO.sub.2--, --C(R.sup.4R.sup.5)-- (provided that R.sup.4 and
R.sup.5 each represent independently a hydrogen atom, an alkyl
group having 1 to 6 carbon atoms, a phenyl group or a
trifluoromethyl group), a substituted or non-substituted
cycloalkylidene group having 6 to 12 carbon atoms, a
9,9'-fluorenylidene group, a 1,8-menthanediyl group, a
2,8-menthanediyl group, a substituted or non-substituted
pyrazylidene group, a substituted or non-substituted arylene group
having 6 to 12 carbon atoms or --C(CH.sub.3).sub.2-ph-C(CH.-
sub.3).sub.2-- (provided that ph represents a phenylene group); and
p represents an integer of 0 to 4) with a carbonic ester-forming
compound.
[0022] (6) The production process for the aromatic polycarbonate
resin as described in the above item (5), wherein a compound
represented by the following Formula [I-6] is used as the divalent
phenol: 5
[0023] wherein R.sup.3, X and p each represent the same as R.sup.3,
X and p in Formula [I-5].
[0024] (7) The production process for the aromatic polycarbonate
resin as described in the above item (5) or (6), wherein the
compound in which R.sup.1 in Formula [I-4] is an alkyl group having
1 to 6 carbon atoms is used as the
2,2-bis(4-hydroxyphenyl)adamantane compound.
[0025] (8) The production process for the aromatic polycarbonate
resin as described in any of the above items (5) to (7), wherein
used as the divalent phenol is the compound in which X in Formula
[I-5] is --C(R.sup.4R.sup.5)-- (provided that R.sup.4 and R.sup.5
each represent independently a hydrogen atom, an alkyl group having
1 to 6 carbon atoms, a phenyl group or a trifluoromethyl group), a
substituted or non-substituted cycloalkylidene group having 6 to 12
carbon atoms or a 9,9'-fluorenylidene group.
[0026] II. Second Invention
[0027] Intensive researches repeated by the present inventors in
order to solve the problems described above have resulted in
finding that the object described above can be achieved by an
aromatic polycarbonate resin obtained by reacting specific divalent
phenols having an adamantane skeleton and constituted by a phenol
group having a substituent with a carbonic ester-forming compound,
and they have come to complete the present second invention based
on the above knowledge.
[0028] That is, the essential point of the second invention is
described below.
[0029] (1) An aromatic polycarbonate resin which comprises a
repetitive unit represented by the following Formula [II-1]: 6
[0030] (wherein R.sup.1 represents a group selected from the group
of a halogen atom, an alkyl group having 1 to 6 carbon atoms, an
alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to
12 carbon atoms, an aryl-substituted alkenyl group having 7 to 13
carbon atoms and a fluoroalkyl group having 1 to 6 carbon atoms;
and m represents an integer of 1 to 4) and in which the solution
having a concentration of 0.5 g/deciliter using methylene chloride
as a solvent has a reduced viscosity (.eta..sub.sp/c) of 0.1
deciliter/g or more which is measured at 20.degree. C.
[0031] (2) The aromatic polycarbonate resin as described in the
above item (1), wherein R.sup.1 in Formula [II-1] is an alkyl group
having 1 to 6 carbon atoms.
[0032] (3) An aromatic polycarbonate resin which comprises a
repetitive unit (II-1) represented by the following Formula [II-2]:
7
[0033] (wherein R.sup.2 represents a group selected from the group
of a halogen atom, an alkyl group having 1 to 6 carbon atoms, an
alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to
12 carbon atoms, an aryl-substituted alkenyl group having 7 to 13
carbon atoms and a fluoroalkyl group having 1 to 6 carbon atoms;
and n is an integer of 1 to 4) and a repetitive unit (II-2)
represented by the following Formula [II-3]: 8
[0034] (wherein R.sup.3 represents a group selected from the group
of a halogen atom, an alkyl group having 1 to 12 carbon atoms, an
alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to
12 carbon atoms, an aryl-substituted alkenyl group having 7 to 13
carbon atoms and a fluoroalkyl group having 1 to 12 carbon atoms; X
represents a single bond, --O--, --CO--, --S--, --SO--,
--SO.sub.2--, --C(R.sup.4R.sup.5)-- (provided that R.sup.4 and
R.sup.5 each represent independently a hydrogen atom, an alkyl
group having 1 to 6 carbon atoms, a phenyl group or a
trifluoromethyl group), a substituted or non-substituted
cycloalkylidene group having 6 to 12 carbon atoms, a
9,9'-fluorenylidene group, a 1,8-menthanediyl group, a
2,8-menthanediyl group, a substituted or non-substituted
pyrazylidene group, a substituted or non-substituted arylene group
having 6 to 12 carbon atoms or --C(CH.sub.3).sub.2-ph-C(CH.-
sub.3).sub.2-- (provided that ph represents a phenylene group); and
p represents an integer of 0 to 4) and in which the solution having
a concentration of 0.5 g/deciliter using methylene chloride as a
solvent has a reduced viscosity (.eta..sub.sp/c) of 0.1 deciliter/g
or more which is measured at 20.degree. C.
[0035] (4) The aromatic polycarbonate resin as described in the
above item (3), wherein the repetitive unit (II-2) is represented
by the following Formula [II-4]: 9
[0036] wherein R.sup.3, X and p each represent the same as R.sup.3,
X and p in Formula [II-3].
[0037] (5) The aromatic polycarbonate resin as described in the
above item (3) or (4), wherein R.sup.2 in Formula [II-2] is an
alkyl group having 1 to 6 carbon atoms.
[0038] (6) The aromatic polycarbonate resin as described in any of
the above items (3) to (5), wherein X in Formula [II-3] is
--C(R.sup.4R.sup.5)-- (provided that R.sup.4 and R.sup.5 each
represent independently a hydrogen atom, an alkyl group having 1 to
6 carbon atoms, a phenyl group or a trifluoromethyl group), a
substituted or non-substituted cycloalkylidene group having 6 to 12
carbon atoms or a 9,9'-fluorenylidene group.
[0039] (7) A production process for the aromatic polycarbonate
resin as described in the above item (1), characterized by reacting
a 1,3-bis(4-hydroxyphenyl)adamantane compound represented by the
following Formula [II-5]: 10
[0040] (wherein R.sup.1 represents a group selected from the group
of a halogen atom, an alkyl group having 1 to 6 carbon atoms, an
alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to
12 carbon atoms, an aryl-substituted alkenyl group having 7 to 13
carbon atoms and a fluoroalkyl group having 1 to 6 carbon atoms;
and m represents an integer of 1 to 4) with a carbonic
ester-forming compound.
[0041] (8) The production process for the aromatic polycarbonate
resin as described in the above item (7), wherein the compound in
which R.sup.1 in Formula [II-5] is an alkyl group having 1 to 6
carbon atoms is used as the 1,3-bis(4-hydroxyphenyl)adamantane
compound.
[0042] (9) A production process for the aromatic polycarbonate
resin as described in the above item (3), characterized by reacting
a 1,3-bis(4-hydroxyphenyl)adamantane compound represented by the
following Formula [II-6]: 11
[0043] (wherein R.sup.2 represents a group selected from the group
of a halogen atom, an alkyl group having 1 to 6 carbon atoms, an
alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to
12 carbon atoms, an aryl-substituted alkenyl group having 7 to 13
carbon atoms and a fluoroalkyl group having 1 to 6 carbon atoms;
and n represents an integer of 1 to 4) and divalent phenol
represented by the following Formula [II-7]: 12
[0044] (wherein R.sup.3 represents a group selected from the group
of a halogen atom, an alkyl group having 1 to 12 carbon atoms, an
alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to
12 carbon atoms, an aryl-substituted alkenyl group having 7 to 13
carbon atoms and a fluoroalkyl group having 1 to 12 carbon atoms; X
represents a single bond, --O--, --CO--, --S--, --SO--,
--SO.sub.2--, --C(R.sup.4R.sup.5)-- (provided that R.sup.4 and
R.sup.5 each represent independently a hydrogen atom, an alkyl
group having 1 to 6 carbon atoms, a phenyl group or a
trifluoromethyl group), a substituted or non-substituted
cycloalkylidene group having 6 to 12 carbon atoms, a
9,9'-fluorenylidene group, a 1,8-menthanediyl group, a
2,8-menthanediyl group, a substituted or non-substituted
pyrazylidene group, a substituted or non-substituted arylene group
having 6 to 12 carbon atoms or --C(CH.sub.3).sub.2-ph-C(CH.-
sub.3).sub.2-- (provided that ph represents a phenylene group); and
p represents an integer of 0 to 4) with a carbonic ester-forming
compound.
[0045] (10) The production process for the aromatic polycarbonate
resin as described in the above item (9), wherein the compound in
which R.sup.2 in Formula [II-6] is an alkyl group having 1 to 6
carbon atoms is used as the 1,3-bis(4-hydroxyphenyl)adamantane
compound.
[0046] (11) The production process for the aromatic polycarbonate
resin as described in the above item (9) or (10), wherein a
compound represented by the following Formula [II-8] is used as the
divalent phenol: 13
[0047] wherein R.sup.3, X and p each represent the same as R.sup.3,
X and p in Formula [II-7].
[0048] (12) The production process for the aromatic polycarbonate
resin as described in any of the above items (9) to (11), wherein
used as the divalent phenol is the compound in which X in Formula
[II-7] is --C(R.sup.4R.sup.5)-- (provided that R.sup.4 and R.sup.5
each represent independently a hydrogen atom, an alkyl group having
1 to 6 carbon atoms, a phenyl group or a trifluoromethyl group), a
substituted or non-substituted cycloalkylidene group having 6 to 12
carbon atoms or a 9,9'-fluorenylidene group.
[0049] III. Third Invention
[0050] Intensive researches repeated by the present inventors in
order to solve the problems described above have resulted in
finding that the object described above can be achieved by using an
aromatic polycarbonate resin comprising a repetitive unit having a
specific adamantane skeleton containing a 2,2-adamantyl group as an
optical part-molding material, and they have come to complete the
present third invention based on the above knowledge.
[0051] That is, the essential point of the third invention is
described below.
[0052] (1) An optical part-molding material comprising an aromatic
polycarbonate resin which comprises a repetitive unit represented
by the following Formula [III-1]: 14
[0053] (wherein R.sup.1 and R.sup.2 each represent independently a
group selected from the group of a halogen atom, an alkyl group
having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon
atoms, an aryl group having 6 to 12 carbon atoms, an
aryl-substituted alkenyl group having 7 to 13 carbon atoms and a
fluoroalkyl group having 1 to 6 carbon atoms; R.sup.3 represents a
group selected from the group of a halogen atom, an alkyl group
having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon
atoms, an aryl group having 6 to 12 carbon atoms, an
aryl-substituted alkenyl group having 7 to 13 carbon atoms and a
fluoroalkyl group having 1 to 12 carbon atoms; a and b represent an
integer of 0 to 4; and c represents an integer of 0 to 14) and in
which the solution having a concentration of 0.5 g/deciliter using
methylene chloride as a solvent has a reduced viscosity
(.eta..sub.sp/c) of 0.1 deciliter/g or more which is measured at
20.degree. C.
[0054] (2) The optical part-molding material as described in the
above item (1), wherein R.sup.1 and R.sup.2 in Formula [III-1] are
alkyl groups having 1 to 6 carbon atoms.
[0055] (3) The optical part-molding material comprising the
aromatic polycarbonate resin as described in the above item (1) or
(2), wherein the repetitive unit is represented by the following
Formula [III-2]: 15
[0056] wherein R.sup.1, R.sup.2, R.sup.3, a, b and c each represent
the same as R.sup.1, R.sup.2, R.sup.3 a, b and c in Formula
[III-1].
[0057] (4) The optical part-molding material as described in the
above item (3), wherein R.sup.1 and R.sup.2 in Formula [III-2] are
alkyl groups having 1 to 6 carbon atoms.
[0058] (5) An optical part-molding material comprising an aromatic
polycarbonate resin which comprises a repetitive unit (III-1)
represented by the following Formula [III-3]: 16
[0059] (wherein R.sup.4 and R.sup.5 each represent independently a
group selected from the group of a halogen atom, an alkyl group
having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon
atoms, an aryl group having 6 to 12 carbon atoms, an
aryl-substituted alkenyl group having 7 to 13 carbon atoms and a
fluoroalkyl group having 1 to 6 carbon atoms; R.sup.6 represents a
group selected from the group of a halogen atom, an alkyl group
having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon
atoms, an aryl group having 6 to 12 carbon atoms, an
aryl-substituted alkenyl group having 7 to 13 carbon atoms and a
fluoroalkyl group having 1 to 12 carbon atoms; d and e represent an
integer of 0 to 4; and f represents an integer of 0 to 14) and a
repetitive unit (III-2) represented by the following Formula
[III-4]: 17
[0060] [wherein R.sup.7 and R.sup.8 each represent independently a
group selected from the group of a halogen atom, an alkyl group
having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon
atoms, an aryl group having 6 to 12 carbon atoms, an
aryl-substituted alkenyl group having 7 to 13 carbon atoms and a
fluoroalkyl group having 1 to 12 carbon atoms; X represents a
single bond, --O--, --CO--, --S--, --SO--, --SO.sub.2--,
--C(R.sup.9R.sup.10)-- (provided that R.sup.9 and R.sup.10 each
represent independently a hydrogen atom, an alkyl group having 1 to
6 carbon atoms, a phenyl group or a trifluoromethyl group), a
substituted or non-substituted cycloalkylidene group having 6 to 12
carbon atoms, a 9,9'-fluorenylidene group, a 1,8-menthanediyl
group, a 2,8-menthanediyl group, a substituted or non-substituted
pyrazylidene group, a substituted or non-substituted arylene group
having 6 to 12 carbon atoms,
--C(CH.sub.3).sub.2-ph-C(CH.sub.3).sub.2-- (provided that ph
represents a phenylene group) or the following Formula [III-5] or
[III-6]: 18
[0061] (wherein R.sup.11 and R.sup.12 each represent independently
a group selected from the group of a halogen atom, an alkyl group
having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon
atoms, an aryl group having 6 to 12 carbon atoms, an
aryl-substituted alkenyl group having 7 to 13 carbon atoms and a
fluoroalkyl group having 1 to 12 carbon atoms; and i and j each
represent an integer of 0 to 14); and g and h each represent an
integer of 0 to 4] and in which the solution having a concentration
of 0.5 g/deciliter using methylene chloride as a solvent has a
reduced viscosity (.eta..sub.sp/c) of 0.1 deciliter/g or more which
is measured at 20.degree. C.
[0062] (6) The optical part-molding material as described in the
above item (5), wherein R.sup.4 and R.sup.5 in Formula [III-3] are
alkyl groups having 1 to 6 carbon atoms.
[0063] (7) The optical part-molding material as described in the
above item (5) or (6), wherein the repetitive unit (III-2) is
represented by the following Formula [III-7]: 19
[0064] wherein R.sup.7, R.sup.8, X, g and h each represent the same
as R.sup.7, R.sup.8, X, g and h in Formula [III-4].
[0065] (8) The optical part-molding material as described in any of
the above items (5) to (7), wherein X in Formula [III-4] is
--C(R.sup.9R.sup.10)-- (provided that R.sup.9 and R.sup.10 each
represent independently a hydrogen atom, an alkyl group having 1 to
6 carbon atoms, a phenyl group or a trifluoromethyl group), a
substituted or non-substituted cycloalkylidene group having 6 to 12
carbon atoms or a 9,9'-fluorenylidene group.
[0066] (9) An optical part prepared by molding the optical
part-molding material as described in any of the above items (1) to
(8).
BEST MODE FOR CARRYING OUT THE INVENTION
[0067] The embodiment of the present invention shall be explained
below.
[0068] I. First Invention
[0069] The first present invention (hereinafter referred to merely
as the .left brkt-top.present invention.right brkt-bot.) relates to
the aromatic polycarbonate resin which comprises the repetitive
unit (I-1) represented by Formula [I-1] described above and the
repetitive unit (I-2) represented by Formula [I-2] described above
and in which the solution having a concentration of 0.5 g/deciliter
using methylene chloride as a solvent has a reduced viscosity
(.eta..sub.sp/c) of 0.1 deciliter/g or more which is measured at
20.degree. C.
[0070] In the above aromatic polycarbonate resin, the alkyl group
having 1 to 6 carbon atoms represented by R.sup.1 in Formula [I-1]
described above includes methyl, ethyl, n-propyl, i-propyl,
n-butyl, i-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl,
cyclopentyl and cyclohexyl. The alkoxy group having 1 to 6 carbon
atoms includes methoxy, ethoxy, n-propoxy, i-propoxy, i-butoxy,
sec-butoxy, tert-butoxy, n-pentyloxy and n-hexyloxy. The aryl group
having 6 to 12 carbon atoms includes phenyl, biphenyl, triphenyl
and naphthyl, and the aryl-substituted alkenyl group having 7 to 13
carbon atoms includes benzyl, phenethyl, styryl and cinnamyl.
Further, the fluoroalkyl group having 1 to 6 carbon atoms includes
monofluoromethyl, difluoromethyl and trifluoromethyl.
[0071] Among the various substituents represented by R.sup.1 in
this Formula [I-1], the alkyl group having 1 to 6 carbon atoms is
preferred because of the excellent heat resistance, and methyl is
more preferred. In addition thereto, among the various substituents
described above, the preferred ones include cyclohexyl, methoxy,
phenyl and trifluoromethyl. In the above Formula [I-1], m may be 0,
that is, it may be a hydrogen atom or may have 1 to 4 substituents.
This m is more preferably 0 to 2.
[0072] The halogen atom represented by R.sup.2 in Formula [I-1]
described above includes a fluorine atom, a chlorine atom, a
bromine atom and an iodine atom. The alkyl group having 1 to 12
carbon atoms represented by R.sup.2 in the above formula includes
methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl,
tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl,
n-undecyl, n-dodecyl, cyclopentyl and cyclohexyl. The alkoxy group
having 1 to 12 carbon atoms includes methoxy, ethoxy, n-propoxy,
i-propoxy, i-butoxy, sec-butoxy, tert-butoxy, n-pentyloxy,
n-hexyloxy, n-heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy,
n-undecyloxy and n-dodecyloxy. The aryl group having 6 to 12 carbon
atoms includes phenyl, biphenyl, triphenyl and naphthyl, and the
aryl-substituted alkenyl group having 7 to 13 carbon atoms includes
benzyl, phenethyl, styryl and cinnamyl. Further, the fluoroalkyl
group having 1 to 12 carbon atoms includes monofluoromethyl,
difluoromethyl and trifluoromethyl. Among the above various
substituents, the preferred ones include methyl, ethyl, methoxy,
ethoxy, phenyl and trifluoromethyl. Further, n in the above Formula
[I-1] may be 0, that is, it may be only a hydrogen atom or may have
any of 1 to 14 substituents.
[0073] In the above aromatic polycarbonate resin, the halogen atom
represented by R.sup.3 in Formula [I-2] described above includes a
fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
The alkyl group having 1 to 12 carbon atoms represented by R.sup.3
in the above formula includes methyl, ethyl, n-propyl, i-propyl,
n-butyl, i-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl,
n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl,
cyclopentyl and cyclohexyl. The alkoxy group having 1 to 12 carbon
atoms includes methoxy, ethoxy, n-propoxy, i-propoxy, i-butoxy,
sec-butoxy, tert-butoxy, n-pentyloxy, n-hexyloxy, n-heptyloxy,
n-octyloxy, n-nonyloxy, n-decyloxy, n-undecyloxy and n-dodecyloxy.
The aryl group having 6 to 12 carbon atoms includes phenyl,
biphenyl, triphenyl and naphthyl, and the aryl-substituted alkenyl
group having 7 to 13 carbon atoms includes benzyl, phenethyl,
styryl and cinnamyl. Further, the fluoroalkyl group having 1 to 12
carbon atoms includes monofluoromethyl, difluoromethyl and
trifluoromethyl. Among the above various substituents, the
preferred ones include methyl, ethyl, cyclohexyl and phenyl.
[0074] In the above aromatic polycarbonate resin, the alkyl group
having 1 to 6 carbon atoms represented by R.sup.4 and R.sup.5 in
Formula [I-2] described above includes methyl, ethyl, n-propyl,
i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, n-pentyl and
n-hexyl. Among them, the suited ones include methyl, ethyl and
n-propyl. Further, the substituted or non-substituted
cycloalkylidene group having 6 to 12 carbon atoms represented by X
in Formula [I-2] includes cyclopentylidene, cyclohexylidene,
cycloheptylidene and cyclooctylidene, and the substituted or
non-substituted arylene group having 6 to 12 carbon atoms includes
phenylene, biphenylene, 1,4-phenylenebis(1-methylethylidene) and
1,3-phenylenebis(1-methylethylidene).
[0075] Further, the aromatic polycarbonate resin in which the
repetitive unit (I-2) has the structural unit represented by
Formula [I-3] is preferred since it is excellent in a heat
resistance and a mechanical strength. The divalent group
represented by X in the above Formulas [I-2] and [I-3] is
preferably --C(R.sup.4R.sup.5)-- (provided that R.sup.4 and R.sup.5
each represent independently a hydrogen atom, an alkyl group having
1 to 6 carbon atoms, a phenyl group or a trifluoromethyl group), a
substituted or non-substituted cycloalkylidene group having 6 to 12
carbon atoms or a 9,9'-fluorenylidene group because of more
excellent heat resistance.
[0076] A content proportion of the repetitive unit (I-1)
represented by Formula [I-1] to the repetitive unit (I-2)
represented by Formula [I-2] each constituting the above aromatic
polycarbonate resin shall not specifically be restricted, and a
content proportion [(I-1)/((I-1)+(I-2))] of the repetitive unit
(I-1) to the whole repetitive units falls preferably in a range of
0.05 to 0.99 in terms of a mole ratio. This is because of the
reasons that if a mole ratio of the above repetitive unit (I-1) is
lower than 0.05, the molding processability is good but the degree
of a rise in the heat resistance is small and that if the above
mole ratio is higher than 0.99, the particularly excellent heat
resistance is shown but the molding processability is reduced in a
certain case because of the low solubility in a solvent. Further,
the content proportion of the above repetitive unit (I-1) to the
whole repetitive units falls particularly preferably in a range of
0.05 to 0.95 because it provides a good balance of the heat
resistance and the mechanical strength with the molding
processability.
[0077] The aromatic polycarbonate resin of the present invention
comprises the repetitive units (I-1) and (I-2), and the solution
having a concentration of 0.5 g/deciliter using methylene chloride
as a solvent has a reduced viscosity (.eta..sub.sp/c) of 0.1
deciliter/g or more which is measured at 20.degree. C. If the above
reduced viscosity is less than 0.1 deciliter/g, the aromatic
polycarbonate resin can not sufficiently obtain a heat resistance
and a mechanical strength. The resin in which the above reduced
viscosity is 0.3 to 3.0 deciliter/g is particularly suited as a
molding material for electric and electronic equipments and optical
equipments.
[0078] Next, the aromatic polycarbonate resin of the present
invention can be produced by a process in which the specific
2,2-bis(4-hydroxyphenyl)ad- amantane compound represented by
Formula [I-4] described above and the divalent phenols represented
by Formula [I-5] described above are reacted with a carbonic
ester-forming compound. In this case, the aromatic polycarbonate
resin can be produced by polymerization by a method in which
interfacial polymerization is carried out in the presence of a
polymerizing solvent, an acid acceptor, an end terminating agent
and a catalyst or a method in which transesterification is carried
out under reduced pressure.
[0079] In the above Formula [I-4], the halogen atom, the alkyl
group, the alkoxy group, the aryl group, the aryl-substituted
alkenyl group and the fluoroalkyl group each represented by R.sup.1
and R.sup.2 include the same ones as the atoms and the groups each
represented by R.sup.1 and R.sup.2 in Formula [I-1] described
above. Further, an alkyl group having 1 to 6 carbon atoms is more
suitably used as R.sup.1 and R.sup.2 in this Formula [I-4].
[0080] The 2,2-bis(4-hydroxyphenyl)adamantane compound represented
by the above Formula [1-4] includes, for example,
2,2-bis(4-hydroxyphenyl)adaman- tane,
2,2-bis(3-methyl-4-hydroxyphenyl)adamantane,
2,2-bis(3-ethyl-4-hydro- xyphenyl)adamantane,
2,2-bis(3-n-propyl-4-hydroxyphenyl)adamantane,
2,2-bis(3-1-propyl-4-hydroxyphenyl)adamantane,
2,2-bis(3-n-butyl-4-hydrox- yphenyl)adamantane,
2,2-bis(3-1-butyl-4-hydroxyphenyl)adamantane,
2,2-bis(3-sec-butyl-4-hydroxyphenyl)adamantane,
2,2-bis(3-tert-butyl-4-hy- droxyphenyl)adamantane,
2,2-bis(3-cyclohexyl-4-hydroxyphenyl)adamantane,
2,2-bis(3-phenyl-4-hydroxyphenyl)adamantane,
2,2-bis(3-chloro-4-hydroxyph- enyl)adamantane,
2,2-bis(3-bromo-4-hydroxyphenyl)adamantane,
2,2-bis(3,5-dimethyl-4-hydroxyphenyl)adamantane,
2,2-bis(3,5-diethyl-4-hy- droxyphenyl)adamantane,
2,2-bis(3,5-dichloro-4-hydroxyphenyl)adamantane and
2,2-bis(3,5-dibromo-4-hydroxyphenyl)adamantane.
[0081] The specific examples of the halogen atom and the alkyl
group represented by X and R.sup.3 in Formula [I-5] include the
same ones as the atoms and the groups represented by X and R.sup.3
in Formula [I-2] described above. The divalent phenols represented
by the above Formula [I-5] include 4,4'-dihydroxybiphenyls such as
4,4'-dihydroxybiphenyl, 3,3'-difluoro-4,4'-dihydroxybiphenyl,
3,3'-dichloro-4,4'-dihydroxybipheny- l,
3,3'-dimethyl-4,4'-dihydroxybiphenyl,
3,3'-diphenyl-4,4'-dihydroxybipph- enyl,
3,3'-dicyclohexyl-4,4'-dihydroxybiphenyl,
2,2'-dimethyl-4,4'-dihydro- xybiphenyl and
3,3',5,5'-tetramethyl-4,4'-dihydroxybiphenyl;
bis(hydroxyphenyl)alkanes such as bis(4-hydroxyphenyl)methane,
bis(4-hydroxyphenyl)dipenylmethane,
bis(4-hydroxyphenyl)phenylmethane,
bis(3-nonyl-4-hydroxyphenyl)methane,
bis(3,5-dimethyl-4-hydroxyphenyl)met- hane,
bis(3,5-dibromo-4-hydroxyphenyl)methane,
bis(3-chloro-4-hydroxypheny- l)methane,
bis(3-fluoro-4-hydroxyphenyl)methane, bis(2-tert-butyl-4-hydrox-
yphenyl)phenylmethane, bis(2-hydroxyphenyl)methane,
bis(2-hydroxyphenyl-4-hydroxyphenyl)methane,
bis(2-hydroxy-4-methylphenyl- )methane,
bis(2-hydroxy-4-methyl-6-tert-butylphenyl)methane,
bis(2-hydroxy-4,6-dimethylphenyl)methane,
1,1-bis(4-hydroxyphenyl)ethane, 1,2-bis(4-hydroxyphenyl)ethane,
1,1-bis(4-hydroxyphenyl)-1-phenylethane,
1,1-bis(4-hydroxy-3-methylphenyl)-1-phenylethane,
1,1-bis(4-hydroxy-3-phe- nylphenyl)-1-phenylethane,
2-(4-hydroxy-3-methylphenyl)-2-(4-hydroxyphenyl- )-1-phenylethane,
1,1-bis(2-tert-butyl-4-hydroxy-3-methylphenyl)ethane,
1-phenyl-1,1-bis(3-fluoro-4-hydroxyphenyl)ethane,
1,1-bis(2-hydroxy-4-met- hylphenyl)ethane,
2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl- )propane,
2,2-bis(2-methyl-4-hydroxyphenyl)propane,
2,2-bis(3-methyl-4-hydroxyphenyl)propane,
2,2-bis(3-isopropyl-4-hydroxyph- enyl)propane,
2,2-bis(3-sec-butyl-4-hydroxyphenyl)propane,
2,2-bis(3-phenyl-4-hydroxyphenyl)propane,
2,2-bis(3-cyclohexyl-4-hydroxyp- henyl)propane,
2,2-bis(3-chloro-4-hydroxyphenyl)propane,
2,2-bis(3-fluoro-4-hydroxyphenyl)propane,
2,2-bis(3-bromo-4-hydroxyphenyl- )propane,
2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane,
1,1-bis(2-tert-butyl-4-hydroxy-5-methylphenyl)propane,
2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane,
2,2-bis(4-hydroxy-3,5-diflu- orophenyl)propane,
2,2-bis(4-hydroxy-3,5-dibromophenyl)propane,
2,2-bis(3-bromo-4-hydroxy-5-chlorophenyl)propane,
2,2-bis(4-hydroxyphenyl- )-1,1,1,3,3,3-hexafluoropropane,
2,2-bis(2-hydroxy-4-sec-butylphenyl)propa- ne,
2,2-bis(2-hydroxy-4,6-dimethylphenyl)propane,
2,2-bis(4-hydroxyphenyl)- butane,
2,2-bis(3-methyl-4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)--
2-methylpropane,
1,1-bis(2-tert-butyl-4-hydroxy-5-methylphenyl)-2-methylpr- opane,
1,1-bis(2-butyl-4-hydroxy-5-methylphenyl)butane,
1,1-bis(2-tert-butyl-4-hydroxy-5-methylphenyl)butane,
1,1-bis(2-methyl-4-hydroxy-5-tert-pentylphenyl)butane,
2,2-bis(4-hydroxy-3,5-dichlorophenyl)butane,
2,2-bis(4-hydroxy-3,5-dibrom- ophenyl)butane,
2,2-bis(4-hydroxyphenyl)-3-methylbutane,
1,1-bis(4-hydroxyphenyl)-3-methylbutane,
3,3-bis(4-hydroxyphenyl)pentane, 2,2-bis(4-hydroxyphenyl)hexane,
2,2-bis(4-hydroxyphenyl)heptane,
2,2-bis(2-tert-butyl-4-hydroxy-5-methylphenyl)heptane,
2,2-bis(4-hydroxyphenyl)octane, 2,2-bis(4-hydroxyphenyl)nonane,
2,2-bis(4-hydroxyphenyl)decane,
1,1-bis(4-hydroxyphenyl)cyclopentane,
1,1-bis(4-hydroxyphenyl)cyclohexane,
1,1-bis(3-methyl-4-hydroxyphenyl)cyc- lohexane,
1,1-bis(4-hydroxy-3,5-dimethylphenyl)cyclohexane,
1,1-bis(3-cyclohexyl-4-hydroxyphenyl)cyclohexane,
1,1-bis(3-phenyl-4-hydr- oxyphenyl)cyclohexane,
1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane and
1,1-bis(3-methyl-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane;
bis(4-hydroxyphenyl) ethers such as bis(4-hydroxyphenyl) ether and
bis(3-fluoro-4-hydroxyphenyl) ether; bis(4-hydroxyphenyl) sulfides;
such as bis(4-hydroxyphenyl) sulfide and
bis(3-methyl-4-hydroxyphenyl) sulfide; bis(4-hydroxyphenyl)
sulfoxides such as bis(4-hydroxyphenyl) sulfoxide and
bis(3-methyl-4-hydroxyphenyl) sulfoxide;
bis(4-hydroxyphenyl)sulfones such as bis(4-hydroxyphenyl)sulfone,
bis(3-methyl-4-hydroxyphenyl)sulfone and
bis(3-phenyl-4-hydroxyphenyl)sul- fone; bis(4-hydroxyphenyl)
ketones such as 4,4'-dihydroxybenzophenone;
bis(hydroxyphenyl)fluorenes such as
9,9-bis(4-hydroxyphenyl)fluorene,
9,9-bis(3-methyl-4-hydroxyphenyl)fluorene and
9,9-bis(3-phenyl-4-hydroxyp- henyl)fluorene; dihydroxy-p-terphenyls
such as 4,4"-dihydroxy-p-terphenyl; dihydroxy-p-quarterphenyls such
as 4,4'"-dihydroxy-p-quarterphenyl; bis(hydroxyphenyl)pyrazines
such as 2,5-bis(4-hydroxyphenyl)pyrazine,
2,5-bis(4-hydroxyphenyl)-3,6-dimethylpyrazine and
2,5-bis(4-hydroxyphenyl- )-2,6-diethylpyrazine;
bis(hydroxyphenyl)menthanes such as
1,8-bis(4-hydroxyphenyl)menthane, 2,8-bis(4-hydroxyphenyl)menthane,
1,8-bis(3-methyl-4-hydroxyphenyl)menthane and
1,8-bis(4-hydroxy-3,5-dimet- hylphenyl)menthane; and
bis[2-(4-hydroxyphenyl)-2-propyl]benzenes such as
1,4-bis[2-(4-hydroxyphenyl)-2-propyl]benzene and
1,3-bis[2-(4-hydroxyphen- yl)-2-propyl]benzene.
[0082] Among the above various divalent phenols, the phenols
represented by Formula [I-6] are preferred, and more suitably used
are the phenols in which the divalent group represented by X in the
above Formulas [I-5] and [I-6] is --C(R.sup.4R.sup.5)-- (provided
that R.sup.4 and R.sup.5 each represent independently a hydrogen
atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group or
a trifluoromethyl group), a substituted or non-substituted
cycloalkylidene group having 6 to 12 carbon atoms or a
9,9'-fluorenylidene group. The divalent phenols having such
chemical structure include, for example,
2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane,
1,1-bis(4-hydroxyphenyl)cyclohexane,
1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane,
9,9-bis(4-hydroxyphenyl)fluorene and
9,9-bis(3-methyl-4-hydroxyphenyl)flu- orene.
[0083] Various dihalogenated carbonyls such as phosgene,
haloformates such as chloroformate and carbonic ester compounds can
be used as the carbonic ester-forming compound described above.
When using the gaseous carbonic ester-forming compound such as
phosgene, a method for blowing it into a reaction system can
suitably be employed. A use proportion of the above carbonic
ester-forming compound is advisably controlled so that it
corresponds to a stoichiometric ratio (equivalent) in this
reaction.
[0084] Solvents used for producing conventional aromatic
polycarbonate resins are used for a solvent used in the above
reaction. The suited solvents include, for example, aromatic
hydrocarbon base solvents such as toluene and xylene, halogenated
hydrocarbons such as methylene chloride, chloroform,
1,1-dichloroethane, 1,2-dichloroethane, 1,1,1-trichloroethane,
1,1,2-trichloroethane, 1,1,1,2-tetrachloroethane,
1,1,2,2-tetrachloroethane, pentachloroethane and chlorobenzene and
acetophenone. The above solvents may be used alone or in
combination of two or more kinds thereof. Further, two kinds of the
solvents which are not miscible with each other may be used.
[0085] Further, capable of being used as the acid acceptor are
metal hydroxides such as sodium hydroxide, potassium hydroxide,
lithium hydroxide and cesium hydroxide, alkaline metal carbonates
such as sodium carbonate and potassium carbonate, organic acids
such as pyridine or mixtures thereof. In respect to a use
proportion of these acid acceptors, considering a stoichiometric
ratio (equivalent) in this reaction, one equivalent of the acid
acceptor per mole of a hydroxyl group of the divalent phenol of the
raw material or a little excess amount over it, preferably 1 to 5
equivalent is advisably used.
[0086] Further, monovalent phenols can be used as the end
terminating agent. Suitably used are, for example,
p-tert-butylphenol, p-phenylphenol, p-cumylphenol,
p-perfluorononylphenol, p-(perfluorononylphenyl)phenol,
p-tert-perfluorobutylphenol and
1-(p-hydroxybenzyl)perfluorodecane.
[0087] Tertiary amines such as triethylamine and quaternary
ammonium salts are suitably used as the catalyst. Further, a method
in which a small amount of an antioxidant such as sodium sulfite
and hydrosulfite is added to carry out the reaction may be adopted
in this reaction system.
[0088] Next, in respect to the reaction conditions in the case of
interfacial polymerization, the reaction temperature is usually 0
to 150.degree. C., preferably 5 to 40.degree. C., and the reaction
pressure may be any of reduced pressure, atmospheric pressure and
applied pressure, but the reaction is carried out preferably at
atmospheric pressure or under applied pressure of a self pressure
level in the reaction system. The reaction time is, though
depending on the reaction temperature, 0.5 minute to 10 hours,
preferably one minute to about 2 hours. This reaction may be
carried out by any reaction system of a continuous method, a
semi-continuous method and a batch method.
[0089] When the reaction is carried out by transesterification, the
reaction is carried out at 120 to 350.degree. C. under reduced
pressure. In this case, the degree of reduced pressure is
strengthened in stages as the reaction goes on, and the pressure is
finally reduced to 1 torr or lower to draw out resulting phenols to
the outside of the reaction system. The reaction time is advisably
controlled to 1 to 4 hours, and the catalyst and the antioxidant
may be added if necessary.
[0090] The aromatic polycarbonate resin thus obtained can be molded
and processed by the same methods as in thermoplastic resins such
as an aromatic polycarbonate resin using publicly known bisphenol A
as a raw material. Further, various additives used in molding and
processing, for example, a heat stabilizer, an antioxidant, a light
stabilizer, a colorant, an anti-static agent, a lubricant and a
mold releasing agent can be blended in suited amounts. The aromatic
polycarbonate resin thus obtained is excellent in a transparency, a
heat resistance and a mechanical strength, and therefore it is
highly useful as a molding material for electric and electronic
equipments and optical equipments, for example, lenses such as a
head lump lens, a prism, an optical fiber, an optical disc and a
panel for display equipments.
[0091] Next, the present invention shall more specifically be
explained with reference to examples and comparative examples.
EXAMPLE I-1
[0092] Methylene chloride 700 ml which was a solvent was added to a
solution prepared by dissolving 45 g of
2,2-bis(4-hydroxyphenyl)adamantan- e and 25 g of
1,1-bis(4-hydroxyphenyl)cyclohexane in 1,360 ml of a potassium
hydroxide aqueous solution having a concentration of 2 normal, and
phosgene gas was blown into the above solution for 30 minutes in a
proportion of 950 ml/minute under cooling while stirring. Then,
this reaction liquid was left standing still and separating, and a
methylene chloride solution of an oligomer having a polymerization
degree of 2 to 5 and having a chloroformate group at a molecular
end was obtained in the organic layer.
[0093] Methylene chloride was added to 110 ml of the methylene
chloride solution thus obtained to control the whole amount to 150
ml, and then a solution prepared by dissolving 5 g of
1,1-bis(4-hydroxyphenyl)cyclohexan- e in 50 ml of a potassium
hydroxide aqueous solution having a concentration of 2 normal was
added thereto. Further, 0.2 g of p-tert-butylphenol was added
thereto as a molecular weight-controlling agent. Then, 1.0 ml of a
triethylamine aqueous solution having a concentration of 7% was
added as a catalyst while vigorously stirring the above mixed
solution to carry out reaction at 25.degree. C. for 1.5 hour under
stirring.
[0094] After finishing the reaction, the reaction product thus
obtained was diluted with one liter of methylene chloride and
washed twice with 1.5 liter of water. Then, it was washed with
hydrochloric acid having a concentration of 0.05 normal and then
further washed twice with one liter of water. The organic layer
thus obtained was thrown into methanol to carry out refining by
reprecipitation, whereby a powder of an aromatic polycarbonate
resin was obtained.
[0095] A solution of the aromatic polycarbonate resin obtained
above having a concentration of 0.5 g/liter using methylene
chloride as a solvent had a reduced viscosity (.eta..sub.sp/c) of
0.6 deciliter/g at 20.degree. C. Further, confirmation of the
structure of the above aromatic polycarbonate resin by .sup.1H-NMR
spectrum analysis resulted in finding that the chemical structure
thereof comprised the following repetitive unit: 20
[0096] Further, a glass transition temperature of the above
aromatic polycarbonate resin was measured to find that it was
238.degree. C. and confirm that it had a very high heat resistance.
Further, a methylene chloride solution of the above aromatic
polycarbonate resin was used to produce a film by casting to find
that it was colorless and highly transparent.
EXAMPLE I-2
[0097] Methylene chloride 700 ml which was a solvent was added to a
solution prepared by dissolving 75 g of
2,2-bis(4-hydroxyphenyl)adamantan- e in 1,360 ml of a potassium
hydroxide aqueous solution having a concentration of 2 normal, and
phosgene gas was blown into the above solution for 30 minutes in a
proportion of 950 ml/minute under cooling while stirring. Then,
this reaction liquid was left standing still and separating, and a
methylene chloride solution of an oligomer having a polymerization
degree of 2 to 5 and having a chloroformate group at a molecular
end was obtained in the organic layer.
[0098] Methylene chloride was added to 110 ml of the methylene
chloride solution thus obtained to control the whole amount to 150
ml, and then a solution prepared by dissolving 6 g of
9,9-bis(3-methyl-4-hydroxyphenyl)f- luorene in 50 ml of a potassium
hydroxide aqueous solution having a concentration of 2 normal was
added thereto. Further, 0.2 g of p-tert-butylphenol was added
thereto as a molecular weight-controlling agent. Then, 1.4 ml of a
triethylamine aqueous solution having a concentration of 7% was
added as a catalyst while vigorously stirring the above mixed
solution to carry out reaction at 25.degree. C. for 1.5 hour under
stirring.
[0099] After finishing the reaction, the reaction product thus
obtained was diluted with 0.5 liter of methylene chloride and
washed twice with 0.5 liter of water. Then, it was washed with
hydrochloric acid having a concentration of 0.01 normal and then
further washed twice with 0.5 liter of water. The organic layer
thus obtained was thrown into methanol to carry out refining by
reprecipitation, whereby a powder of an aromatic polycarbonate
resin was obtained.
[0100] A solution of the aromatic polycarbonate resin obtained
above having a concentration of 0.5 g/liter using methylene
chloride as a solvent had a reduced viscosity (.eta..sub.sp/c) of
0.5 deciliter/g at 20.degree. C. Further, confirmation of the
structure of the above aromatic polycarbonate resin by .sup.1H-NMR
spectrum analysis resulted in finding that the chemical structure
thereof comprised the following repetitive unit: 21
[0101] Further, a glass transition temperature of the above
aromatic polycarbonate resin was measured to find that it was
282.degree. C. and confirm that it had a very high heat resistance.
Further, a methylene chloride solution of the above aromatic
polycarbonate resin was used to produce a film by casting to find
that it was colorless and highly transparent.
EXAMPLE I-3
[0102] Methylene chloride 900 ml which was a solvent was added to a
solution prepared by dissolving 170 g of
1,1-bis(4-hydroxyphenyl)cyclohex- ane in 1,530 ml of a potassium
hydroxide aqueous solution having a concentration of 2 normal, and
phosgene gas was blown into the above solution for 30 minutes in a
proportion of 950 ml/minute under cooling while stirring. Then,
this reaction liquid was left standing still and separating, and a
methylene chloride solution of an oligomer having a polymerization
degree of 2 to 5 and having a chloroformate group at a molecular
end was obtained in the organic layer.
[0103] Methylene chloride was added to 110 ml of the methylene
chloride solution thus obtained to control the whole amount to 150
ml, and then a solution prepared by dissolving 6 g of
2,2-bis(3,5-dimethyl-4-hydroxyphen- yl)adamantane in 50 ml of a
potassium hydroxide aqueous solution having a concentration of 2
normal was added thereto. Further, 0.2 g of p-tert-butylphenol was
added thereto as a molecular weight-controlling agent. Then, 1.0 ml
of a triethylamine aqueous solution having a concentration of 7%
was added as a catalyst while vigorously stirring the above mixed
solution to carry out reaction at 25.degree. C. for 1.5 hour under
stirring.
[0104] After finishing the reaction, the reaction product thus
obtained was diluted with 0.5 liter of methylene chloride and
washed twice with 0.5 liter of water. Then, it was washed with
hydrochloric acid having a concentration of 0.01 normal and then
further washed twice with 0.5 liter of water. The organic layer
thus obtained was thrown into methanol to carry out refining by
reprecipitation, whereby a powder of an aromatic polycarbonate
resin was obtained.
[0105] A solution of the aromatic polycarbonate resin obtained
above having a concentration of 0.5 g/liter using methylene
chloride as a solvent had a reduced viscosity (.eta..sub.sp/c) of
0.4 deciliter/g at 20.degree. C. Further, confirmation of the
structure of the above aromatic polycarbonate resin by .sup.1H-NMR
spectrum analysis resulted in finding that the chemical structure
thereof comprised the following repetitive unit: 22
[0106] Further, a glass transition temperature of the above
aromatic polycarbonate resin was measured to find that it was
207.degree. C. and confirm that it had a very high heat resistance.
Further, a methylene chloride solution of the above aromatic
polycarbonate resin was used to produce a film by casting to find
that it was colorless and highly transparent.
COMPARATIVE EXAMPLE I-1
[0107] The same procedure as in Example I-2 was repeated, except
that in Example I-2, 5 g of 2,2-bis(4-hydroxyphenyl)adamantane was
added in place of 6 g of 9,9-bis(3-methyl-4-hydroxyphenyl)fluorene
added at the latter stage.
[0108] A solution of the aromatic polycarbonate resin obtained
above having a concentration of 0.5 g/liter using methylene
chloride as a solvent had a reduced viscosity (.eta..sub.sp/c) of
0.5 deciliter/g at 20.degree. C. Further, confirmation of the
structure of the above aromatic polycarbonate resin by .sup.1H-NMR
spectrum analysis resulted in finding that the chemical structure
thereof comprised the following repetitive unit: 23
[0109] Further, a glass transition temperature of the above
aromatic polycarbonate resin was measured to find that it was
298.degree. C. and confirm that it had a very high heat resistance.
However, a film produced by casting using a methylene chloride
solution of the above aromatic polycarbonate resin was whitened due
to crystallization and, so that it had a low transparency.
[0110] II. Second Invention
[0111] The aromatic polycarbonate resin of the present invention is
an aromatic polycarbonate resin which comprises the repetitive unit
represented by Formula [II-1] described above and in which the
solution having a concentration of 0.5 g/deciliter using methylene
chloride as a solvent has a reduced viscosity (.eta..sub.sp/c) of
0.1 deciliter/g or more which is measured at 20.degree. C.
[0112] In the above aromatic polycarbonate resin, the halogen atom
represented by R.sup.1 in Formula [II-1] described above includes a
fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
The alkyl group having 1 to 6 carbon atoms represented by R.sup.1
in the above formula includes methyl, ethyl, n-propyl, i-propyl,
n-butyl, i-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl,
cyclopentyl and cyclohexyl. The alkoxy group having 1 to 6 carbon
atoms includes methoxy, ethoxy, n-propoxy, i-propoxy, i-butoxy,
sec-butoxy, tert-butoxy, n-pentyloxy and n-hexyloxy. The aryl group
having 6 to 12 carbon atoms includes phenyl, biphenyl, triphenyl
and naphthyl, and the aryl-substituted alkenyl group having 7 to 13
carbon atoms includes benzyl, phenethyl, styryl and cinnamyl.
Further, the fluoroalkyl group having 1 to 6 carbon atoms includes
monofluoromethyl, difluoromethyl and trifluoromethyl. Further, the
resin in which m in Formula [II-1] described above is 1 to 4 can be
used, and the resin in which m 1 to 2 is more preferred. When m is
2 or more, respective R.sup.1 may be the same of different.
[0113] The aromatic polycarbonate resin of the resin present
invention in which R.sup.1 in Formula [II-1] described above is an
alkyl group having 1 to 6 carbon atoms is particularly preferred
since it is excellent in a heat resistance.
[0114] Also, the aromatic polycarbonate resin of a copolymer type
according to the present invention is an aromatic polycarbonate
resin which comprises the repetitive unit (II-1) represented by
Formula [II-2] described above and the repetitive unit (II-2)
represented by Formula [II-3] described above and in which the
solution having a concentration of 0.5 g/deciliter using methylene
chloride as a solvent has a reduced viscosity (.eta..sub.sp/c) of
0.1 deciliter/g or more which is measured at 20.degree. C.
[0115] In the above aromatic polycarbonate resin, the halogen atom,
the alkyl group, the alkoxy group, the aryl group, the
aryl-substituted alkenyl group and the fluoroalkyl group each
represented by R.sup.2 in Formula [II-2] include the same ones as
those each represented by R.sup.1 in Formula [I-1] described above.
Also, the resin in which n in Formula [II-2] described above is 1
to 4 is used, and the resin in which n 1 to 2 is more preferred.
Further, the aromatic polycarbonate resin comprising the repetitive
unit (II-1) in which R.sup.2 in Formula [II-2] described above is
an alkyl group having 1 to 6 carbon atoms is preferred since it is
excellent in a heat resistance.
[0116] Also, the halogen atom represented by R.sup.3 in Formula
[II-3] includes a fluorine atom, a chlorine atom, a bromine atom
and an iodine atom. The alkyl group having 1 to 12 carbon atoms
includes methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl,
sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl,
n-nonyl, n-decyl, n-undecyl, n-dodecyl, cyclopentyl and cyclohexyl.
The alkoxy group having 1 to 12 carbon atoms includes methoxy,
ethoxy, n-propoxy, i-propoxy, i-butoxy, sec-butoxy, tert-butoxy,
n-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, n-nonyloxy,
n-decyloxy, n-undecyloxy and n-dodecyloxy. The aryl group having 6
to 12 carbon atoms includes phenyl, biphenyl, triphenyl and
naphthyl, and the aryl-substituted alkenyl group having 7 to 13
carbon atoms includes benzyl, phenethyl, styryl and cinnamyl.
Further, the fluoroalkyl group having 1 to 12 carbon atoms includes
monofluoromethyl, difluoromethyl and trifluoromethyl. Among the
above various substituents, the preferred ones include methyl,
ethyl, methoxy, ethoxy, phenyl and trifluoromethyl. Further, p in
Formula [II-3] may be 0, that is, it may be only a hydrogen atom or
may have any of 1 to 4 substituents.
[0117] Given are the resins in which X in the above Formula [II-3]
is a single bond, --O--, --CO--, --S--, --SO--, --SO.sub.2--,
--C(R.sup.4R.sup.5)-- (provided that R.sup.4 and R.sup.5 each
represent independently a hydrogen atom, an alkyl group having 1 to
6 carbon atoms, a phenyl group or a trifluoromethyl group), a
substituted or non-substituted cycloalkylidene group having 6 to 12
carbon atoms, a 9,9'-fluorenylidene group, a 1,8-menthanediyl
group, a 2,8-menthanediyl group, a substituted or non-substituted
pyrazylidene group, a substituted or non-substituted arylene group
having 6 to 12 carbon atoms or
--C(CH.sub.3).sub.2-ph-C(CH.sub.3).sub.2-- (provided that ph
represents a phenylene group). Among them, the resins in which X is
--C(R.sup.4R.sup.5)-(provided that R.sup.4 and R.sup.5 each
represent independently a hydrogen atom, an alkyl group having 1 to
6 carbon atoms, a phenyl group or a trifluoromethyl group), a
substituted or non-substituted cycloalkylidene group having 6 to 12
carbon atoms or a 9,9'-fluorenylidene group are preferred since
they are excellent in a heat resistance.
[0118] In this regard, the alkyl group having 1 to 6 carbon atoms
represented by R.sup.4 and R.sup.5 described above in
--C(R.sup.4R.sup.5)-- represented by X includes the same ones as
the alkyl groups having 1 to 6 carbon atoms represented by R.sup.1
described above. Also, the substituted or non-substituted
cycloalkylidene group having 6 to 12 carbon atoms represented by X
includes cyclopentylidene, cyclohexylidene,
3,3,5-trimethylcyclohexylidene, cycloheptylidene and
cyclooctylidene, and the substituted or non-substituted arylene
group having 6 to 12 carbon atoms includes phenylene, biphenylene,
1,4-phenylenebis(1-methylethylidene) and
1,3-phenylenebis(1-methylethylid- ene).
[0119] Further, the above repetitive unit (II-2) constituting the
aromatic polycarbonate resin has preferably a structure containing
a p-phenylene group represented by Formula [II-4] since the resin
is excellent in a heat resistance and a mechanical strength.
[0120] Next, a content proportion of the repetitive unit (II-1) to
the repetitive unit (II-2) each constituting the above aromatic
polycarbonate resin of a copolymer type shall not specifically be
restricted, and a content proportion [(II-1)/((II-1)+(II-2))] of
the repetitive unit (II-1) to the whole repetitive units falls
preferably in a range of 0.05 to 0.99 in terms of a mole ratio.
This is because of the reasons that if a mole ratio of the above
repetitive unit (II-1) is lower than 0.05, the moldability is good
but the degree of a rise in the heat resistance is small and that
if the above mole ratio is higher than 0.99, the excellent heat
resistance is shown but the solubility in a solvent is low and the
moldability is reduced. Further, the above content proportion of
the repetitive unit (II-1) to the whole repetitive units falls
preferably in a range of 0.05 to 0.95 because it provides a good
balance of the heat resistance and the mechanical strength with the
molding processability.
[0121] In the aromatic polycarbonate resin of the present
invention, the solution having a concentration of 0.5 g/deciliter
using methylene chloride as a solvent has a reduced viscosity
(.eta..sub.sp/c) of 0.1 deciliter/g or more which is measured at
20.degree. C. This is because if the above reduced viscosity is
less than 0.1 deciliter/g, the aromatic polycarbonate resin can not
sufficiently obtain a heat resistance and a mechanical strength.
The resin in which the above reduced viscosity is 0.3 to 3.0
deciliter/g is particularly suited as a molding material for
electric and electronic equipments and optical equipments.
[0122] Next, the aromatic polycarbonate resin of the present
invention can be produced by a process in which the
1,3-bis(4-hydroxyphenyl)adamantane compound represented by Formula
[II-5] described above is reacted with a carbonic ester-forming
compound. Further, the aromatic polycarbonate resin of a copolymer
type can be produced by a process in which the
1,3-bis(4-hydroxyphenyl)adamantane compound represented by Formula
[II-6] described above and the divalent phenols represented by
Formula [II-7] described above are reacted with a carbonic
ester-forming compound. In carrying out these reactions, the
aromatic polycarbonate resin can be produced by a method in which
interfacial polymerization is carried out in the presence of a
polymerizing solvent, an acid acceptor, an end terminating agent
and a catalyst or a method in which transesterification is carried
out under reduced pressure.
[0123] In Formulas [II-5] and [II-6], the halogen atom, the alkyl
group, the alkoxy group, the aryl group, the aryl-substituted
alkenyl group and the fluoroalkyl group each represented by R.sup.1
to R.sup.6 include the same ones as the atoms and the groups each
represented by R.sup.1 in Formula [II-1] described above. In this
regard, the 1,3-bis(4-hydroxyphenyl)adamantane compound represented
by the above Formulas [II-5] and [II-6] includes, for example,
1,3-bis(3-chloro-4-hydr- oxyphenyl)adamantane,
1,3-bis(3-bromo-4-hydroxyphenyl)adamantane,
1,3-bis(3-fluoro-4-hydroxyphenyl)adamantane,
1,3-bis(3-methyl-4-hydroxyph- enyl)adamantane,
1,3-bis(3-ethyl-4-hydroxyphenyl)adamantane,
1,3-bis(3-n-propyl-4-hydroxyphenyl)adamantane,
1,3-bis(3-1-propyl-4-hydro- xyphenyl)adamantane,
1,3-bis(3-n-butyl-4-hydroxyphenyl)adamantane,
1,3-bis(3-1-butyl-4-hydroxyphenyl)adamantane,
1,3-bis(3-sec-butyl-4-hydro- xyphenyl)adamantane,
1,3-bis(3-tert-butyl-4-hydroxyphenyl)adamantane,
1,3-bis(3-n-pentyl-4-hydroxyphenyl)adamantane,
1,3-bis(3-n-hexyl-4-hydrox- yphenyl)adamantane,
1,3-bis(3-cyclohexyl-4-hydroxyphenyl)adamantane,
1,3-bis(3-methoxy-4-hydroxyphenyl)adamantane,
1,3-bis(3-ethoxy-4-hydroxyp- henyl)adamantane,
1,3-bis(3-phenyl-4-hydroxyphenyl)adamantane,
1,3-bis(3-benzyl-4-hydroxyphenyl)adamantane,
1,3-bis(3-naphthyl-4-hydroxy- phenyl)adamantane,
1,3-bis(3-tetrafluormethyl-4-hydroxyphenyl)adamantane,
1,3-bis(3,5-dichloro-4-hydroxyphenyl)adamantane,
1,3-bis(3,5-dibromo-4-hy- droxyphenyl)adamantane,
1,3-bis(3,5-difluoro-4-hydroxyphenyl)adamantane,
1,3-bis(3,5-dimethyl-4-hydroxyphenyl)adamantane,
1,3-bis(3,5-diethyl-4-hy- droxyphenyl)adamantane,
1,3-bis(3,5-dimethoxy-4-hydroxyphenyl)adamantane and
1,3-bis(3,5-diethoxy-4-hydroxyphenyl)adamantane.
[0124] The halogen atom, the alkyl group, the alkoxy group, the
aryl group, the aryl-substituted alkenyl group and the fluoroalkyl
group each represented by X and R.sup.3 in Formula [II-7] described
above include the same ones as the atoms and the groups each
represented by X and R.sup.3 in Formula [II-3] described above. The
compounds given as the examples of the divalent phenols represented
by Formula [1-5] in the first invention apply to the above divalent
phenols represented by Formula [II-7].
[0125] The phenol represented by Formula [II-8] described above is
suitably used as the divalent phenol used for producing the
aromatic polycarbonate resin of the present invention. Further, the
divalent phenol in which X in Formulas [II-7] and [II-8] described
above is --C(R.sup.4R.sup.5)-- (provided that R.sup.4 and R.sup.5
each represent independently a hydrogen atom, an alkyl group having
1 to 6 carbon atoms, a phenyl group or a trifluoromethyl group), a
substituted or non-substituted cycloalkylidene group having 6 to 12
carbon atoms or a 9,9'-fluorenylidene group is preferably used
since the aromatic polycarbonate resin which is excellent in a heat
resistance and a mechanical strength is obtained. The suitable
divalent phenols having such chemical structure include, for
example, 2,2-bis(4-hydroxyphenyl)pro- pane,
2,2-bis(4-hydroxyphenyl)butane,
1,1-bis(4-hydroxyphenyl)cyclohexane,
1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane,
9,9-bis(4-hydroxyphenyl)fluorene and
9,9-bis(3-methyl-4-hydroxyphenyl)flu- orene.
[0126] Also, the compounds given in the first invention apply to
the carbonic ester-forming compound described above. When using the
gaseous carbonic ester-forming compound such as phosgene, a method
for blowing it into a reaction system can suitably be adopted.
[0127] Solvents used for producing conventional aromatic
polycarbonate resins are used for a solvent used in the above
reaction, and the solvents given in the first invention apply
thereto. The above solvents may be used alone or in combination of
two or more kinds thereof. Further, two kinds of the solvents which
are not miscible with each other may be used.
[0128] Also, those described in the first invention apply as they
are to the acid acceptor, the end terminating agent and the
catalyst.
[0129] Further, those described in the first invention also apply
as they are to the reaction conditions in the case of interfacial
polymerization or the reaction conditions in the case of
transesterification.
[0130] Those described in the first invention also apply as they
are to molding and processing of the aromatic polycarbonate resin
thus obtained and various additives used therein.
[0131] The aromatic polycarbonate resin thus obtained is excellent
in a transparency, a heat resistance and a mechanical strength, and
therefore it is highly useful as a molding material for electric
and electronic equipments and optical equipments, for example,
lenses such as a head lump lens, a prism, an optical fiber, an
optical disc and a panel for display equipments.
[0132] Next, the present invention shall more specifically be
explained with reference to examples and comparative examples.
EXAMPLE II-1
[0133] Methylene chloride 900 ml which was a solvent was added to a
solution prepared by dissolving 170 g of
1,1-bis(4-hydroxyphenyl)cyclohex- ane in 1,530 ml of a potassium
hydroxide aqueous solution having a concentration of 2 normal, and
phosgene gas was blown into the above solution for 30 minutes in a
proportion of 950 ml/minute under cooling while stirring. Then,
this reaction liquid was left standing still and separating, and a
methylene chloride solution of an oligomer having a polymerization
degree of 2 to 5 and having a chloroformate group at a molecular
end was obtained in the organic layer.
[0134] Methylene chloride was added to 110 ml of the methylene
chloride solution thus obtained to control the whole amount to 150
ml, and then a solution prepared by dissolving 5.5 g of
1,3-bis(4-hydroxyphenyl)adamanta- ne in 50 ml of a potassium
hydroxide aqueous solution having a concentration of 2 normal was
added thereto. Further, 0.2 g of p-tert-butylphenol was added
thereto as a molecular weight-controlling agent. Then, 1.0 ml of a
triethylamine aqueous solution having a concentration of 7% was
added as a catalyst while vigorously stirring the above mixed
solution to carry out reaction at 25.degree. C. for 1.5 hour under
stirring.
[0135] After finishing the reaction, the reaction product thus
obtained was diluted with 0.5 liter of methylene chloride and
washed twice with 0.5 liter of water. Then, it was washed with 0.5
liter of hydrochloric acid having a concentration of 0.01 normal
and then further washed twice with 0.5 liter of water. The organic
layer thus obtained was thrown into methanol to carry out refining
by reprecipitation, whereby an aromatic polycarbonate resin was
obtained.
[0136] A solution of the aromatic polycarbonate resin obtained
above having a concentration of 0.5 g/deciliter using methylene
chloride as a solvent had a reduced viscosity (.eta..sub.sp/c) of
0.4 deciliter/g at 20.degree. C. Further, confirmation of the
structure of the above aromatic polycarbonate resin by .sup.1H-NMR
spectrum analysis resulted in finding that the chemical structure
thereof comprised the following repetitive unit: 24
[0137] Further, a glass transition temperature of the above
aromatic polycarbonate resin was measured to find that it was
189.degree. C. and confirm that it had a very high heat resistance.
Further, a methylene chloride solution of the above aromatic
polycarbonate resin was used to produce a film by casting to find
that it was colorless and highly transparent.
EXAMPLE II-2
[0138] The same procedure as in Example II-1 was repeated, except
that 6 g of 1,3-bis(3,5-dimethyl-4-hydroxyphenyl)adamantane was
added in place of 1,3-bis(4-hydroxyphenyl)adamantane which was the
raw material used in Example II-1.
[0139] A solution of the aromatic polycarbonate resin obtained
above having a concentration of 0.5 g/deciliter using methylene
chloride as a solvent had a reduced viscosity (.eta..sub.sp/c) of
0.5 deciliter/g at 20.degree. C. Further, confirmation of the
structure of the above aromatic polycarbonate resin by .sup.1H-NMR
spectrum analysis resulted in finding that the chemical structure
thereof comprised the following repetitive unit: 25
[0140] Further, a glass transition temperature of the above
aromatic polycarbonate resin was measured to find that it was
196.degree. C. and confirm that it had a very high heat resistance.
Further, a methylene chloride solution of the above aromatic
polycarbonate resin was used to produce a film by casting to find
that it was colorless and highly transparent.
EXAMPLE II-3
[0141] Methylene chloride 900 ml which was a solvent was added to a
solution prepared by dissolving 170 g of
2,2-bis(4-hydroxyphenyl)propane in 1,530 ml of a potassium
hydroxide aqueous solution having a concentration of 2 normal, and
phosgene gas was blown into the above solution for 30 minutes in a
proportion of 950 ml/minute under cooling while stirring. Then,
this reaction liquid was left standing still and separating, and a
methylene chloride solution of an oligomer having a polymerization
degree of 2 to 5 and having a chloroformate group at a molecular
end was obtained in the organic layer.
[0142] Methylene chloride was added to 110 ml of the methylene
chloride solution thus obtained to control the whole amount to 150
ml, and then a solution prepared by dissolving 5.5 g of
1,3-bis(3,5-dimethyl-4-hydroxyph- enyl)adamantane in 50 ml of a
potassium hydroxide aqueous solution having a concentration of 2
normal was added thereto. Further, 0.2 g of p-tert-butylphenol was
added thereto as a molecular weight-controlling agent. Then, 1.0 ml
of a triethylamine aqueous solution having a concentration of 7%
was added as a catalyst while vigorously stirring the above mixed
solution to carry out reaction at 25.degree. C. for 1.5 hour under
stirring.
[0143] After finishing the reaction, the reaction product thus
obtained was diluted with 0.5 liter of methylene chloride and
washed twice with 0.5 liter of water. Then, it was washed with 0.5
liter of hydrochloric acid having a concentration of 0.01 normal
and then further washed twice with 0.5 liter of water. The organic
layer thus obtained was thrown into methanol to carry out refining
by reprecipitation, whereby an aromatic polycarbonate resin was
obtained.
[0144] A solution of the aromatic polycarbonate resin obtained
above having a concentration of 0.5 g/deciliter using methylene
chloride as a solvent had a reduced viscosity (.eta..sub.sp/c) of
0.4 deciliter/g at 20.degree. C. Further, confirmation of the
structure of the above aromatic polycarbonate resin by .sup.1H-NMR
spectrum analysis resulted in finding that the chemical structure
thereof comprised the following repetitive unit: 26
[0145] Further, a glass transition temperature of the above
aromatic polycarbonate resin was measured to find that it was
170.degree. C. and confirm that it had a high heat resistance.
Further, a methylene chloride solution of the above aromatic
polycarbonate resin was used to produce a film by casting to find
that it was colorless and highly transparent.
COMPARATIVE EXAMPLE II-1
[0146] Only 1,1-bis(4-hydroxyphenyl)cyclohexane was used as the
divalent phenol of the raw material to produce an aromatic
polycarbonate resin by conventional interfacial polymerization.
[0147] A solution of the aromatic polycarbonate resin obtained
above having a concentration of 0.5 g/deciliter using methylene
chloride as a solvent had a reduced viscosity (.eta..sub.sp/c) of
0.4 deciliter/g at 20.degree. C. It was confirmed that the chemical
structure of the above aromatic polycarbonate resin comprised the
following repetitive unit: 27
[0148] Further, a glass transition temperature of the above
aromatic polycarbonate resin was measured to find that it was
170.degree. C.
[0149] III. Third Invention
[0150] The optical part-molding material of the present invention
comprises the aromatic polycarbonate resin which comprises the
repetitive unit represented by Formula [III-1] or Formula [III-2]
described above and in which the solution having a concentration of
0.5 g/deciliter using methylene chloride as a solvent has a reduced
viscosity (.eta..sub.sp/c) of 0.1 deciliter/g or more which is
measured at 20.degree. C. or the aromatic polycarbonate resin which
comprises the repetitive unit (III-1) represented by Formula
[III-3] described above and the repetitive unit (III-2) represented
by Formula [III-4] or Formula [III-7] described above and in which
the solution having a concentration of 0.5 g/deciliter using
methylene chloride as a solvent has a reduced viscosity
(.eta..sub.sp/c) of 0.1 deciliter/g or more which is measured at
20.degree. C.
[0151] In the repetitive unit represented by Formula [III-1] or
Formula [III-2] which is the structural unit for the above aromatic
polycarbonate resin, the halogen atom represented by R.sup.1 and
R.sup.2 includes a fluorine atom, a chlorine atom, a bromine atom
and an iodine atom. The alkyl group having 1 to 6 carbon atoms
represented by R.sup.1 and R.sup.2 includes methyl, ethyl,
n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl,
n-pentyl, n-hexyl, cyclopentyl and cyclohexyl. The alkoxy group
having 1 to 6 carbon atoms includes methoxy, ethoxy, n-propoxy,
i-propoxy, n-butoxy, i-butoxy, sec-butoxy, tert-butoxy, n-pentyloxy
and n-hexyloxy. The aryl group having 6 to 12 carbon atoms includes
phenyl, biphenyl and naphthyl, and the aryl-substituted alkenyl
group having 7 to 13 carbon atoms includes benzyl, phenethyl,
styryl and cinnamyl. Further, the fluoroalkyl group having 1 to 12
carbon atoms includes monofluoromethyl, difluoromethyl and
trifluoromethyl. Further, a and b may be 0, that is, it may be only
a hydrogen atom or may have 1 to 4, preferably 1 to 2
substituents.
[0152] Further, the aromatic polycarbonate resin in which R.sup.1
and R.sup.2 in Formula [III-1] or Formula [III-2] are the alkyl
groups having 1 to 6 carbon atoms is preferred as a molding
material for optical parts since it is excellent in an heat
resistance. Among the above alkyl groups having 1 to 6 carbon
atoms, methyl is more preferred.
[0153] In Formula [III-1] described above, the halogen atom
represented by R.sup.3 includes the same ones as in R.sup.1 and
R.sup.2 described above. The alkyl group having 1 to 12 carbon
atoms represented by R.sup.3 includes methyl, ethyl, n-propyl,
i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, n-pentyl,
n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl,
cyclopentyl and cyclohexyl. The alkoxy group having 1 to 12 carbon
atoms includes methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy,
i-butoxy, sec-butoxy, tert-butoxy, n-pentyloxy, n-hexyloxy,
n-heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, n-undecyloxy and
n-dodecyloxy. The aryl group having 6 to 12 carbon atoms includes
phenyl, biphenyl and naphthyl, and the aryl-substituted alkenyl
group having 7 to 13 carbon atoms includes benzyl, phenethyl,
styryl and cinnamyl. Further, the fluoroalkyl group having 1 to 12
carbon atoms includes monofluoromethyl, difluoromethyl and
trifluoromethyl. Among the above various substituents, methyl,
ethyl, methoxy, ethoxy, phenyl and trifluoromethyl are particularly
preferred. Further, c may be 0, that is, it may be only a hydrogen
atom or may have 1 to 14 substituents.
[0154] In Formula [III-3], the halogen atom, the alkyl group, the
alkoxy group, the aryl group, the aryl-substituted alkenyl group
and the fluoroalkyl group each represented by R.sup.4, R.sup.5 and
R.sup.6 include the same ones as the atoms and the groups each
represented by R.sup.1, R.sup.2 and R.sup.3 described above.
[0155] In Formula [III-4], the halogen atom, the alkyl group, the
alkoxy group, the aryl group, the aryl-substituted alkenyl group
and the fluoroalkyl group each represented by R.sup.7 and R.sup.8
include the same ones as the atoms and the groups each represented
by R.sup.3 described above. X in the above Formula [III-4] includes
a single bond, --O--, --CO--, --S--, --SO--, --SO.sub.2--,
--C(R.sup.9R.sup.10)-- (provided that R.sup.9 and R.sup.10 each
represent independently a hydrogen atom, an alkyl group having 1 to
6 carbon atoms, a phenyl group or a trifluoromethyl group), a
substituted or non-substituted cycloalkylidene group having 6 to 12
carbon atoms, a 9,9'-fluorenylidene group, a 1,8-menthanediyl
group, a 2,8-menthanediyl group, a substituted or non-substituted
pyrazylidene group, a substituted or non-substituted arylene group
having 6 to 12 carbon atoms, --C(CH.sub.3).sub.2-ph-C(CH.su-
b.3).sub.2-- (provided that ph represents a phenylene group) or a
substituted or non-substituted adamantyl group represented by
Formula [III-5] or Formula [III-6]. The halogen atom, the alkyl
group, the alkoxy group, the aryl group, the aryl-substituted
alkenyl group and the fluoroalkyl group each represented by
R.sup.11 and R.sup.12 in the above Formula [III-5] and Formula
[III-6] include the same ones as the atoms and the groups each
represented by R.sup.3 described above. Further, i and j may be 0
or it may have 1 to 14 substituents.
[0156] In this regard, the alkyl group having 1 to 6 carbon atoms
represented by R.sup.9 and R.sup.10 described above includes the
ones as in R.sup.1 and R.sup.2 described above. Further, the
substituted or non-substituted cycloalkylidene group having 6 to 12
carbon atoms represented by X includes cyclopentylidene,
cyclohexylidene and cyclooctylidene, and the substituted or
non-substituted arylene group having 6 to 12 carbon atoms includes
phenylene, biphenylene, naphthylene,
1,4-phenylenebis(1-methylethylidene) and
1,3-phenylenebis(1-methylethylid- ene). In the above Formula
[III-4], g and h may be 0 or it may have 1 to 4 substituents.
[0157] Further, the resin in which X in the above Formulas [III-4]
is --C(R.sup.9R.sup.10)-- (provided that R.sup.9 and R.sup.10 each
represent independently a hydrogen atom, an alkyl group having 1 to
6 carbon atoms, a phenyl group or a trifluoromethyl group), a
substituted or non-substituted cycloalkylidene group having 6 to 12
carbon atoms or a 9,9'-fluorenylidene group is preferred since it
is excellent in an optical property, a heat resistance and a
mechanical strength.
[0158] The aromatic polycarbonate resin in which the repetitive
unit (III-2) has the structural unit represented by Formula [III-7]
is preferred since it is excellent in a heat resistance and a
mechanical strength.
[0159] A content proportion of the repetitive unit (III-1) to the
repetitive unit (III-2) each constituting the above aromatic
polycarbonate resin shall not specifically be restricted, and a
content proportion [(III-1)/((III-1)+(III-2))] of the repetitive
unit (III-1) to the whole repetitive units falls preferably in a
range of 0.05 to 0.99 in terms of a mole ratio. This is because of
the reasons that if a mole ratio of the above repetitive unit
(III-1) is lower than 0.05, the molding processability is good but
the degree of a rise in the heat resistance is small in a certain
case and that if the above mole ratio is higher than 0.99, the
particularly excellent heat resistance is shown but the molding
processability is reduced in a certain case. In the case of the
above aromatic polycarbonate resin of a copolymer type, the content
proportion of the above repetitive unit (III-1) to the whole
repetitive units falls particularly preferably in a range of 0.05
to 0.95 because it provides a good balance of the heat resistance
and the mechanical strength with the moldability.
[0160] The aromatic polycarbonate resin used for the optical
part-molding material of the present invention is a resin in which
the solution having a concentration of 0.5 g/deciliter using
methylene chloride as a solvent has a reduced viscosity
(.eta..sub.sp/c) of 0.1 deciliter/g or more which is measured at
20.degree. C. This is because of the reasons that if the above
reduced viscosity is less than 0.1 deciliter/g, the aromatic
polycarbonate resin can not sufficiently obtain a heat resistance
and a mechanical strength and that characteristics required to the
molding material for optical parts can not sufficiently be
satisfied. The aromatic polycarbonate resin in which a reduced
viscosity is 0.3 to 3.0 deciliter/g is particularly suited as the
molding material for optical equipment parts.
[0161] Next, the aromatic polycarbonate resin used in the present
invention can be produced by a process in which a
2,2-bis(hydroxyphenyl)a- damantane compound alone or the same and
the divalent phenols are reacted with a carbonic ester-forming
compound. In this case, it can be produced by a method in which
interfacial polymerization is carried out in the presence of a
polymerizing solvent, an acid acceptor, an end terminating agent
and a catalyst or a method in which transesterification is carried
out under reduced pressure.
[0162] The adamantane compound used for producing the above
aromatic polycarbonate resin includes, for example,
2,2-bis(4-hydroxyphenyl)adaman- tane,
2,2-bis(3-hydroxyphenyl)adamantane,
2,2-bis(3-chloro-4-hydroxyphenyl- )adamantane,
2,2-bis(3-bromo-4-hydroxyphenyl)adamantane,
2,2-bis(3-fluoro-4-hydroxyphenyl)adamantane,
2,2-bis(3-methyl-4-hydroxyph- enyl)adamantane,
2,2-bis(3-ethyl-4-hydroxyphenyl)adamantane,
2,2-bis(3-n-propyl-4-hydroxyphenyl)adamantane,
2,2-bis(3-1-propyl-4-hydro- xyphenyl)adamantane,
2,2-bis(3-n-butyl-4-hydroxyphenyl)adamantane,
2,2-bis(3-1-butyl-4-hydroxyphenyl)adamantane,
2,2-bis(3-sec-butyl-4-hydro- xyphenyl)adamantane,
2,2-bis(3-tert-butyl-4-hydroxyphenyl)adamantane,
2,2-bis(3-n-pentyl-4-hydroxyphenyl)adamantane,
2,2-bis(3-n-hexyl-4-hydrox- yphenyl)adamantane,
2,2-bis(3-cyclohexyl-4-hydroxyphenyl)adamantane,
2,2-bis(3-methoxy-4-hydroxyphenyl)adamantane,
2,2-bis(3-ethoxy-4-hydroxyp- henyl)adamantane,
2,2-bis(3-phenyl-4-hydroxyphenyl)adamantane,
2,2-bis(3-benzyl-4-hydroxyphenyl)adamantane,
2,2-bis(3-naphthyl-4-hydroxy- phenyl)adamantane,
2,2-bis(3-tetrafluormethyl-4-hydroxyphenyl)adamantane,
2,2-bis(3,5-dichloro-4-hydroxyphenyl)adamantane,
2,2-bis(3,5-dibromo-4-hy- droxyphenyl)adamantane,
2,2-bis(3,5-difluoro-4-hydroxyphenyl)adamantane,
2,2-bis(3,5-dimethyl-4-hydroxyphenyl)adamantane,
2,2-bis(3,5-diethyl-4-hy- droxyphenyl)adamantane,
2,2-bis(3,5-dimethoxy-4-hydroxyphenyl)adamantane and
2,2-bis(3,5-diethoxy-4-hydroxyphenyl)adamantane. The above
2,2-bis(hydroxyphenyl)adamantane compounds may be used in
combination of two or more kinds thereof.
[0163] The divalent phenol used for producing the above aromatic
polycarbonate resin includes 4,4'-dihydroxybiphenyls;
bis(hydroxyphenyl)alkanes; bis(4-hydroxyphenyl) ethers;
bis(4-hydroxyphenyl) sulfides; bis(4-hydroxyphenyl) sulfoxides;
bis(4-hydroxyphenyl)sulfones; bis(4-hydroxyphenyl) ketones;
bis(hydroxyphenyl)fluorenes; dihydroxy-p-terphenyls;
dihydroxy-p-quarterphenyls; bis(hydroxyphenyl)pyrazines;
bis(hydroxyphenyl)menthanes; and
bis[2-(4-hydroxyphenyl)-2-propyl]benzene- s, all of which have been
given as the examples in the first invention. Further, it includes
1,3-bis(4-hydroxyphenyl)adamantane,
1,3-bis(3-chloro-4-hydroxyphenyl)adamantane and
1,3-bis(3-methyl-4-hydrox- yphenyl)adamantane.
[0164] Also, the compounds given in the first invention apply to
the carbonic ester-forming compound described above. When using the
gaseous carbonic ester-forming compound such as phosgene, a method
for blowing it into a reaction system can suitably be adopted.
[0165] Solvents used for producing conventional aromatic
polycarbonate resins are used for a solvent used in the above
reaction, and the solvents given in the first invention apply
thereto. The above solvents may be used alone or in combination of
two or more kinds thereof. Further, two kinds of the solvents which
are not miscible with each other may be used.
[0166] Also, those described in the first invention apply as they
are to the acid acceptor, the end terminating agent and the
catalyst.
[0167] Further, those described in the first invention also apply
as they are to the reaction conditions in the case of interfacial
polymerization or the reaction conditions in the case of
transesterification.
[0168] Those described in the first invention also apply as they
are to molding and processing of the optical part-molding material
comprising the aromatic polycarbonate resin thus obtained and
various additives used therein.
[0169] The optical part-molding material of the present invention
has an excellent transparency and is excellent in a heat
resistance, a mechanical strength and a dimensional stability, and
therefore it is highly useful as a molding material for an optical
disc substrate such as a digital audio disc, a digital video disc
and an optical memory disc, various lenses such as a lens for an
optical pickup, spectacle lenses, contact lenses and a lens sheet,
an optical sheet substrate such as a prism, a mirror, an optical
fiber, a liquid crystal display and a portable key sheet and an
optical functional element such as a light guiding substance, a
reflection film, a light scattering sheet, a polarizing plate and a
phase difference plate.
[0170] Next, the present invention shall more specifically be
explained with reference to examples and comparative examples.
EXAMPLE III-1
[0171] (1) Production of an Optical Part-Molding Material
[0172] Methylene chloride 700 ml which was a solvent was added to a
solution prepared by dissolving 45 g of
2,2-bis(4-hydroxyphenyl)adamantan- e and 25 g of
1,1-bis(4-hydroxyphenyl)cyclohexane in 1,360 ml of a potassium
hydroxide aqueous solution having a concentration of 2 normal, and
phosgene gas was blown into the above solution for 30 minutes in a
proportion of 950 ml/minute under cooling while stirring. Then,
this reaction liquid was left standing still and separating, and a
methylene chloride solution of an oligomer having a polymerization
degree of 2 to 5 and having a chloroformate group at a molecular
end was obtained in the organic layer.
[0173] Methylene chloride was added to 110 ml of the methylene
chloride solution thus obtained to control the whole amount to 150
ml, and then a solution prepared by dissolving 5 g of
1,1-bis(4-hydroxyphenyl)cyclohexan- e in 50 ml of a potassium
hydroxide aqueous solution having a concentration of 2 normal was
added thereto. Further, 0.2 g of p-tert-butylphenol was added
thereto as a molecular weight-controlling agent. Then, 1.0 ml of a
triethylamine aqueous solution having a concentration of 7% was
added as a catalyst while vigorously stirring the above mixed
solution to carry out reaction at 25.degree. C. for 1.5 hour under
stirring.
[0174] After finishing the reaction, the reaction product thus
obtained was diluted with one liter of methylene chloride and
washed twice with 1.5 liter of water. Then, it was washed with
hydrochloric acid having a concentration of 0.05 normal and then
further washed twice with one liter of water. The organic layer
thus obtained was thrown into methanol to carry out refining by
reprecipitation, whereby a powder of an aromatic polycarbonate
resin was obtained.
[0175] A solution of the aromatic polycarbonate resin obtained
above having a concentration of 0.5 g/liter using methylene
chloride as a solvent had a reduced viscosity (.eta..sub.sp/c) of
0.6 deciliter/g at 20.degree. C. Further, confirmation of the
structure of the above aromatic polycarbonate resin by .sup.1H-NMR
spectrum analysis resulted in finding that the chemical structure
thereof comprised the following repetitive unit: 28
[0176] (2) Evaluation of the Optical Part-Molding Material
[0177] A solution having a concentration of 20 mass % which was
prepared by dissolving the aromatic polycarbonate resin obtained in
(1) described above in methylene chloride was cast on a glass
substrate and left standing for a half day or longer, and then a
film formed on the glass substrate was peeled off from the glass
substrate. Then, this film was heated in a vacuum dryer at
70.degree. C. for 2 hours and then at 100.degree. C. for 12 hours,
whereby the transparent film having a thickness of 0.1 mm was
obtained.
[0178] (2-1) Heat Resistance
[0179] The aromatic polycarbonate resin film obtained above was
heated from 25.degree. C. up to 350.degree. C. at a heating speed
of 10.degree. C./minute under nitrogen flow (20 ml/minute) by means
of DSC220 manufactured by Seiko Electron Co., Ltd. and immediately
quenched to remove a heat history of the sample, and a glass
transition temperature thereof was further measured at the same
heating speed according to JIS K7121. As a result thereof, it was
found that the above aromatic polycarbonate resin had a glass
transition temperature of 238.degree. C.
[0180] (2-2) Transparency
[0181] A test piece having a length of 40 mm and a width of 40 mm
was cut out from the aromatic polycarbonate resin film obtained
above, and this test piece was measured for a haze (%) by means of
HGM-2DP type haze meter manufactured by Suga Test Instruments Co.,
Ltd. As a result thereof, it was found that the above aromatic
polycarbonate resin film had a haze of 0.3%.
[0182] (2-3) Retardation
[0183] A test piece having a length of 40 mm and a width of 40 mm
was cut out from the aromatic polycarbonate resin film obtained
above, and this test piece was measured for a phase difference at a
wavelength of 15 nm by means of a polarizing microspectrophotometer
by a rotary polarizer method (Semonalmon method). As a result
thereof, it was found that the above aromatic polycarbonate resin
film had a retardation of 4 nm.
[0184] (2-4) Refractive Index
[0185] A test piece having a length of 20 mm and a width of 10 mm
was cut out from the aromatic polycarbonate resin film obtained
above, and this test piece was measured for a refractive index by
means of an Abbe's refractometer manufactured by Atago Co., Ltd. As
a result thereof, it was found that the above aromatic
polycarbonate resin film had a refractive index of 1.584.
EXAMPLE III-2
[0186] (1) Production of an Optical Part-Molding Material
[0187] Methylene chloride 700 ml which was a solvent was added to a
solution prepared by dissolving 75 g of
2,2-bis(4-hydroxyphenyl)adamantan- e in 1,360 ml of a potassium
hydroxide aqueous solution having a concentration of 2 normal, and
phosgene gas was blown into the above solution for 30 minutes in a
proportion of 950 ml/minute under cooling while stirring. Then,
this reaction liquid was left standing still and separating, and a
methylene chloride solution of an oligomer having a polymerization
degree of 2 to 5 and having a chloroformate group at a molecular
end was obtained in the organic layer.
[0188] Methylene chloride was added to 110 ml of the methylene
chloride solution thus obtained to control the whole amount to 150
ml, and then a solution prepared by dissolving 6 g of
9,9-bis(3-methyl-4-hydroxyphenyl)f- luorene in 50 ml of a potassium
hydroxide aqueous solution having a concentration of 2 normal was
added thereto. Further, 0.2 g of p-tert-butylphenol was added
thereto as a molecular weight-controlling agent. Then, 1.4 ml of a
triethylamine aqueous solution having a concentration of 7% was
added as a catalyst while vigorously stirring the above mixed
solution to carry out reaction at 25.degree. C. for 1.5 hour under
stirring.
[0189] After finishing the reaction, the reaction product thus
obtained was diluted with 0.5 liter of methylene chloride and
washed twice with 0.5 liter of water. Then, it was washed with
hydrochloric acid having a concentration of 0.01 normal and then
further washed twice with 0.5 liter of water. The organic layer
thus obtained was thrown into methanol to carry out refining by
reprecipitation, whereby a powder of an aromatic polycarbonate
resin was obtained.
[0190] A solution of the aromatic polycarbonate resin obtained
above having a concentration of 0.5 g/liter using methylene
chloride as a solvent had a reduced viscosity (.eta..sub.sp/c) of
0.5 deciliter/g at 20.degree. C. Further, confirmation of the
structure of the above aromatic polycarbonate resin by .sup.1H-NMR
spectrum analysis resulted in finding that the chemical structure
thereof comprised the following repetitive unit: 29
[0191] (2) Evaluation of the Optical Part-Molding Material
[0192] The aromatic polycarbonate resin obtained in (1) described
above was subjected to the evaluation of an aromatic polycarbonate
resin film in the same manner as in (2) of Example III-1. The
results thereof are shown in Table III-1.
EXAMPLE III-3
[0193] Methylene chloride 900 ml which was a solvent was added to a
solution prepared by dissolving 170 g of
1,1-bis(4-hydroxyphenyl)cyclohex- ane in 1,530 ml of a potassium
hydroxide aqueous solution having a concentration of 2 normal, and
phosgene gas was blown into the above solution for 30 minutes in a
proportion of 950 ml/minute under cooling while stirring. Then,
this reaction liquid was left standing still and separating, and a
methylene chloride solution of an oligomer having a polymerization
degree of 2 to 5 and having a chloroformate group at a molecular
end was obtained in the organic layer.
[0194] Methylene chloride was added to 110 ml of the methylene
chloride solution thus obtained to control the whole amount to 150
ml, and then a solution prepared by dissolving 6 g of
2,2-bis(3,5-dimethyl-4-hydroxyphen- yl)adamantane in 50 ml of a
potassium hydroxide aqueous solution having a concentration of 2
normal was added thereto. Further, 0.2 g of p-tert-butylphenol was
added thereto as a molecular weight-controlling agent. Then, 1.0 ml
of a triethylamine aqueous solution having a concentration of 7%
was added as a catalyst while vigorously stirring the above mixed
solution to carry out reaction at 25.degree. C. for 1.5 hour under
stirring.
[0195] After finishing the reaction, the reaction product thus
obtained was diluted with 0.5 liter of methylene chloride and
washed twice with 0.5 liter of water. Then, it was washed with
hydrochloric acid having a concentration of 0.01 normal and then
further washed twice with 0.5 liter of water. The organic layer
thus obtained was thrown into methanol to carry out refining by
reprecipitation, whereby a powder of an aromatic polycarbonate
resin was obtained.
[0196] A solution of the aromatic polycarbonate resin obtained
above having a concentration of 0.5 g/liter using methylene
chloride as a solvent had a reduced viscosity (n.sub.sp/c) of 0.4
deciliter/g at 20.degree. C. Further, confirmation of the structure
of the above aromatic polycarbonate resin by .sup.1H-NMR spectrum
analysis resulted in finding that the chemical structure thereof
comprised the following repetitive unit: 30
[0197] (2) Evaluation of the Optical Part-Molding Material
[0198] The aromatic polycarbonate resin obtained in (1) described
above was subjected to the evaluation of the aromatic polycarbonate
resin film in the same manner as in (2) of Example III-1. The
results thereof are shown in Table III-1.
COMPARATIVE EXAMPLE III-1
[0199] A film was obtained by the same casting method as in Example
III-1, except that used was an aromatic polycarbonate resin
(reduced viscosity (.eta..sub.sp/c)=0.5 deciliter/g) produced by a
publicly known interfacial polymerization method using
2,2-bis(4-hydroxyphenyl)-propane as a raw material. The aromatic
polycarbonate resin obtained above was subjected to the evaluation
of an aromatic polycarbonate resin film in the same manner as in
(2) of Example III-1. The results thereof are shown in Table III-1
(in the table, .left brkt-top.Example III-l.right brkt-bot. is
shown as .left brkt-top.Example 1.right brkt-bot. for convenience,
and the same shall apply to the other examples and comparative
examples).
1 TABLE III-1 Example Comparative 1 2 3 Example 1 Thickness (mm)
0.1 0.1 0.1 0.1 Glass 238 282 207 145 transition temperature
(.degree. C.) Retardation (nm) 4 3 5 11 Haze (%) 0.3 0.2 0.2 0.3
Refractive index 1.584 1.590 1.578 1.585
INDUSTRIAL APPLICABILITY
[0200] According to the present invention, capable of being
provided are an aromatic polycarbonate resin which is excellent in
a transparency, a heat resistance and a mechanical strength and
which has a good moldability, an effective production process for
the same, an optical part-molding material which is excellent in an
optical characteristic and a mechanical strength and which has a
particularly high heat resistance and an optical part prepared by
molding the same.
* * * * *